EP0775182A1 - A method for the extraction of low molecular weight mercaptans from petroleum and gas condensates - Google Patents
A method for the extraction of low molecular weight mercaptans from petroleum and gas condensatesInfo
- Publication number
- EP0775182A1 EP0775182A1 EP95925985A EP95925985A EP0775182A1 EP 0775182 A1 EP0775182 A1 EP 0775182A1 EP 95925985 A EP95925985 A EP 95925985A EP 95925985 A EP95925985 A EP 95925985A EP 0775182 A1 EP0775182 A1 EP 0775182A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal hydroxide
- petroleum
- catalyst
- aqueous solution
- cobalt
- 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- Withdrawn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
- 239000003208 petroleum Substances 0.000 title claims abstract description 26
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000605 extraction Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 34
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010779 crude oil Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 239000002184 metal Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 37
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 32
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 22
- 239000003921 oil Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 14
- 238000000746 purification Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012264 purified product Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group 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 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DVIPPHSQIBKWSA-UHFFFAOYSA-N 4-chlorophthalic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1C(O)=O DVIPPHSQIBKWSA-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/96—Water
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of extraction of low molecular weight mercaptans from petroleum (e.g., crude oil) or gas condensate containing such mercaptans comprises (1) contacting the mercaptans with oxygen in an aqueous solution of a metal hydroxyde, in the presence of a cobalt dihalodihydroxydisulfophthalocyanine catalyst, the catalyst being used in an amount within the range of from about 0.5 x 10-5 to about 2.5 x 10-5 weight percent based on the weight of the petroleum or gas condensate, the catalyst being introduced into the crude oil or gas condensate continuously in the form of a catalytic complex in an aqueous solution of a metal hydroxide, the extraction method being conducted at a temperature ranging from about 40 to about 60 °C and a pressure ranging from about 1.0 to about 1.4 MPa, and (2) separating the petroleum or gas condensate fro m the aqueous solution of metal hydroxyde.
Description
A METHOD FOR THE EXTRACTION OF LOW MOLECULAR WEIGHT MERCAPTANS FROM PETROLEUM AND GAS CONDENSATES
BACKGROUND OF THE INVENTION
The present invention relates to petrochemistry, specifically to a method for the extraction of mercaptans from petroleum and gas condensates, and may find application in the petroleum, natural gas, petroleum-processing and petrochemical industry.
Known methods for the extraction of mercaptan from oil and gas condensates involve their treatment with an 18 to 25% aqueous solution of an alkali metal hydroxide, ethyl alcohol, ketone and formaldehyde, with the subsequent release of the purified product (see Russian Author's Certificates Nos. 1567598 and 1579927 issued in 1990).
Another known method for the extraction of mercaptan from gas condensates is by a process which involves treatment with a sodium salt of arylsulfinic acid with the subsequent release of the purified product (see Russian Author's Certificate No. 1810377 issued in 1993.)
The principal drawbacks of the known methods consist in the great amount of scarce and costly reagents which must be consumed in the process (namely, ketones, aldehydes, sulfinic acids) , since during the extraction of the mercaptan from the raw material, the cited reagents which are applied enter into a permanent, irreversible reaction with the mercaptan, resulting in the formation of
unregenerable organic compounds containing oxygen and sulfur.
A method is also known for the extraction of mercaptan from petroleum and petroleum byproducts by means of processing the raw material with a cuprate of the naphthene in the oil with the weight ratio of the copper salt to the mercaptan in the raw material falling within the range of from 3 to 4:1 (see Russian Author's Certificate No. 1616959 issued in 1990.)
The principal disadvantages of the aforesaid method are: the high rate of consumption of the scarce reagent involved, especially when purifying petroleum with a high content of sour sulfur (mercaptan sulfur) , the difficulty of separating the resulting precipitate from the purified product, the formation of a waste byproduct (a precipitate) which is difficult to utilize, as well as the loss of the purified product together with the discarded residue.
The method which most closely resembles the method of the present invention both in its technological essence and the obtained result is a method for the extraction of mercaptans from petroleum distillates by processing with the oxygen of the air in an aqueous solution of an alkali metal hydroxide, in the presence of a cobalt octocarboxytetraphenylphthalocyanine catalyst, in an amount of 0.005 to 0.2 weight percent, as calculated with respect to the aqueous solution of the alkali metal hydroxide (see Russian Author's Certificate No. 1824421 issued in 1991). The principal disadvantages of this method are to be found in the insufficiently high degree of mercaptan extraction from the raw material as well as the low stability of the catalytic activity of the catalyst.
it is an object of the present invention to increase the degree to which the raw material is purified and the mercaptan extracted, to increase the stability of the catalytic activity of the catalyst under the conditions of the purification of petroleum and gas condensate.
SUMMARY OF THE INVENTION
in accordance with the present invention, there is provided a method of extraction of low molecular weight mercaptans from petroleum or gas condensate containing such low molecular weight mercaptans comprising (1) contacting the mercaptans with oxygen in an aqueous solution of a metal hydroxide, in the presence of a cobalt dihalodihydroxydisulfophthalocyanine catalyst, the catalyst being used in an amount within the range of from about 0.5 x ιo*5 to about 2.5 x 10"5 weight percent based on the weight of the petroleum or gas condensate, the catalyst being introduced into the petroleum or gas condensate continuously in the form of a catalytic complex in an aqueous solution of a metal hydroxide, the extraction method being conducted at temperature ranging from about 40 to about 60°C and a pressure ranging from about 1.0 to about 1.4 MPa, and (2) separating the petroleum or gas condensate from the aqueous solution of metal hydroxide.
Also provided in accordance with this invention is the above-described extraction method wherein the catalytic complex has been prepared by dissolving cobalt dihalodihydroxydisulfo-phthalocyanine in an aqueous solution of a metal hydroxide comprising about 1 weight percent metal hydroxide, based on the combined weight of the metal hydroxide and water, with the subsequent adjustment of the
concentration of the metal hydroxide upwards to a level of about 2 to about 20 weight percent.
The present invention further provides cobalt dihalodihydroxy-disulfophthalocyanines having the general formula:
where R is -OH, Rt is halogen and R2 is -S03H.
The distinguishing features of the method of the present invention are to be found in the use of the cobalt dihalo- dihydroxydisulfophthalocyanine as the catalyst, the continuous introduction of the catalyst into the petroleum or gas condensate in the form of a catalytic complex in an aqueous solution of a metal hydroxide, the manner of preparation of the catalytic complex which is to be used,
and the preferred conditions for the performance of the process.
The aforesaid distinguishing characteristics of the proposed method define its novelty and the level of the invention, as compared to the established state-of-the-art, since the application of the cobalt dihalodihydroxydisulfophthalocyanine, with its continuous introduction into the raw material in the form of a catalytic complex, in an aqueous solution of a metal hydroxide, for the purpose of treating petroleum and gas condensates has not been described in the literature, whereas it permits the process to be carried out with a higher degree of mercaptan oxidation, under conditions involving the prolonged use of the catalyst with a decrease in the rate of its consumption.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides a method of treating petroleum, e.g. whole crude oil, or gas condensates which contain low molecular weight mercaptans to convert the low molecular weight mercaptans to disulfides. As used herein, the term "low molecular weight mercaptans" refers to mercaptans in the C1-C3 range.
The method of this invention employs a cobalt dihalo- dihydroxydisulfophthalocyanine catalyst. This catalyst has the following general formula:
09
10 where R is -OH, R, is halogen (e.g., -Cl or -Br) and Rj is -
11 S03H. The position of the substituents on the
! phthalocyanine structure is not believed to be critical.
13 Also, the formula above depicts the compound as having two
14 each of -OH, halogen and -S03H groups on the phthalocyanine
15 structure. This represents the average number of these
16 substituents in the molecule. In actual practice, any given
17 molecule of the catalyst may contain 1-3 -OH groups, 2-4
18 halogens and 1-3 -S03H groups. For economic reasons, the -■9 preferred halogen is chlorine, though bromine may also be 20 Used.
21
22 The proposed use of the cobalt dihalodihydroxydisulfo-
23 phthalocyanine in an amount falling within the range of from
24 about 0.5 x 10"5 to about 2.5 x 10"5 weight percent, based on
25 the weight of the petroleum or gas condensate to be
26 purified, is both necessary and sufficient. This is because
27 if n amount less than 0.5 x 10"J weight percent is used, the
28 necessary thoroughness of purification will not be achieved;
29 on the other hand, if the amount used is greater than 2.5 x 3^ 10'5 weight percent, such an increase does not bring about an
31 improvement in the thoroughness of the extraction and
32 becomes economically unjustifiable. 33
34
The use of a continuous flow of the catalyst in the form of a catalytic complex in an aqueous solution of a metal hydroxide, instead of a single step of loading the catalyst into the system, permits the stability of the catalytic effect of the metal hydroxide solution to be retained for a prolonged period of time, with a corresponding reduction in the rate of catalyst consumption.
The catalyst of this invention is dissolved in an aqueous solution of an metal hydroxide. Examples of suitable metal hydroxides include the alkali metal hydroxides and alkaline earth metal hydroxides. The preferred metal hydroxides are the alkali metal hydroxides, with sodium hydroxide being particularly preferred. The concentration of the metal hydroxide in the solution used to treat the petroleum or gas condensate should be from about 2 to about 20 weight percent, based on the weight of the metal hydroxide and water. However, it has been found that the cobalt dihalodihydroxydisulfophthalocyanine catalyst of this invention does not readily dissolve either in water or in a strongly alkaline aqueous solution. Therefore, it is preferred to dissolve the catalyst in a weakly alkaline aqueous solution, e.g., one containing about one weight percent metal hydroxide, and then raise the metal hydroxide concentration in the resulting catalyst-containing solution to the desired level of from about 2 to about 20 weight percent.
The proposed method has been successfully tested on a pilot installation with a capacity of 2 tons/hr, using crude oil and gas condensate from the Tengiz formation as a test sample. The method shall now be described with reference to the following examples.
Example 1
The extraction of low molecular weight mercaptans from oil is carried out using a pilot installation, which consists of a cavity to be used for the preparation of the catalytic complex, a reaction column, a settling tank for the separation of the treated oil from the alkaline solution, and pump to be used to supply the solution to a mixer.
The initial crude oil, the air, and the catalytic complex together with the aqueous solution of an alkali metal hydroxide which is circulating through the system are continuously fed to the mixer, and from there to the reaction column. The obtained products are fed from the reaction column into the settling tank, taking off treated oil from the top of the column and the circulating alkaline solution from the bottom. The alkaline solution then returns to the mixer and is reused.
The continuous supply of the catalytic complex to the mixer is performed by means of a dosing pump, from the cavity which is to be used to prepare the catalytic complex.
The preparation of the catalytic complex of cobalt dihalo- dihydroxydisulfophthalocyanine in an aqueous solution of an alkali metal hydroxide is carried out according to the following procedure. 1.6 Grams of cobalt dichlorodihydroxydisulfo-phthalocyanine is dissolved in two liters of a 1 weight percent aqueous solution of an alkali metal hydroxide. Once the catalyst has been completely dissolved, the concentration of the alkali metal hydroxide is adjusted upwards to a level of 20 weight percent. The obtained catalyst solution is introduced into the reaction system at a rate of 0.2 liter/hr. During this time, the
01 concentration of the catalyst constitutes 1 x 10"5 weight
02 percent, based on the weight of the crude oil. 03
04 The experimental conditions are: 05
06 -- rate of oil consumption; 2 m3/hr, or 1600 tons/hr;
07 -_ rate of circulation of the alkaline solution; 0.2
08 ton/hr;
09 -- rate of consumption of the alkaline solution of the -10 catalyst: 0.2 I/hr;
11 .. concentration of the alkali: 20 weight percent;
12 -_ air consumption: 1.2 nm3/hr;
13 -- temperature of the process: 50°C;
14 -- pressure of the process: 1.2 MPa;
15 __. quantity of the circulating alkaline solution of the
16 catalyst in the system: 800 kg;
17 -_ initial quantity of methylmercaptan and ethylmercaptan
18 in the crude oil adds up to 400 ppm (0.04 weight
19 percent) . 20
21 According to the experimental process, every four hours
22 samples of treated crude oil are taken and analyzed for
23 methylmercaptan and ethylmercaptan content by
24 chromatographic method, using a "Tsvet-500" chromatograph
25 with a flame-photometric detector. The results of the
26 experiment are presented in the Table below. 27
28 Example 2 29
30 Under the same conditions as those described in Example 1,
31 crude oil is subjected to purification with the continuous
3 supply of the catalytic complex of cobalt
33 dichlorodihydroxydisulfo-phthalocyanine in an aqueous 4 solution of an alkali metal hydroxide, prepared as in the
case of Example 1, at a rate of 0.1 liter per hour. In this case, the concentration of catalyst is 0.5 x 10"3 weight percent. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan The results of the experiment are given in the Table below.
Example 3
Under the same conditions as those described in Example 1, crude oil is subjected to purification with the continuous supply of the catalytic complex of cobalt dichlorodihydroxydisulfo-phthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.5 liter per hour. In this case, the concentration of catalyst is 2.5 x 10"5 weight percent. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Example 4
Under the same conditions as those described in Example 1, gas condensate is subjected to purification with the continuous supply of the catalytic complex of cobalt dichlorodihydroxy-disulfophthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.1 liter per hour. In this case, the concentration of catalyst is 0.5 x 10"5 weight percent. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Example 5
Under the same conditions as those described in Example 1, crude oil is subjected to purification with the continuous supply of the catalytic complex of cobalt dichlorodihydroxydisulfo-phthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.5 liter per hour. In this case, the concentration of catalyst is 2.5 x 10"5 weight percent. For this experiment, the temperature of the process is maintained at 40°C. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Example 6
Under the same conditions as those described in Example 1, oil is subjected to purification with the continuous supply of the catalytic complex of cobalt dichlorodihydroxydisulfo- phthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.5 liter per hour. In this case, the concentration of catalyst in terms of the oil is 2.5 x 10"s weight percent. For this experiment, the temperature of the process is maintained at 60°C. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Exam le 7
Under the same conditions as those described in Example 1, gas condensate is subjected to purification with the
continuous supply of the catalytic complex of cobalt dichlorodihydroxy-disulfophthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.1 liter per. hour. In this case, the concentration of catalyst is 0.5 x 10"5 weight percent. For this experiment, the pressure of the system is maintained at 1.0 MPa Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Example 8
Under the same conditions as those described in Example 1, gas condensate is subjected to purification with the continuous supply of the catalytic complex of cobalt dichlorodihydroxy-disulfophthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.1 liter per hour. In this case, the concentration of catalyst is 0.5 x 10s weight percent. For this experiment, the pressure of the system is maintained at 1.4 MPa Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Comparative Example A
Under the same conditions as those described in Example 1, oil is subjected to purification with a single-step of loading the reaction system with the catalytic complex of cobalt dichloro-dihydroxydisulfophthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.1 liter per hour. In this
case, the concentration of catalyst comprises 2.5 x 10'3 weight percent. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
Comparative Example B
Under the same conditions as those described in Example 1, oil is subjected to purification with the continuous supply of the catalytic complex of octacarboxytetraphenylphthalocyanine in an aqueous solution of an alkali metal hydroxide, prepared as in the case of Example 1, at a rate of 0.5 liter per hour. In this case, the concentration of catalyst is 2.5 x 10'5 weight percent. Every four hours, a sample of treated oil is removed and analyzed for the presence of methylmercaptan and ethylmercaptan. The results of the experiment are given in the Table below.
As can be seen from the Table below, the use of the catalyst of this invention (e.g., Example 3), as compared to the known catalyst (Comparative Example B) , under conditions of their continuous introduction into the raw material supply allows the degree of extraction of low molecular weight mercaptans from the crude oil and gas condensate to be increased by 15 to 20%.
The continuous introduction into the reaction mixture of cobalt dichlorodihydroxydisulfophthalocyanine as a catalytic complex in an aqueous solution of an alkali metal hydroxide (Examples 1, 2, 3), as compared to its introduction by loading in a single operation loading (Comparative Example A) , allows the degree of extraction of low molecular weight
mercaptans from crude oil and gas condensate to be increased by 30%.
The cited advantages of the catalyst of this invention as well as of the method of its introduction into the reaction system, allow the necessary degree of extraction of low molecular weight mer- captans from crude oil and gas condensate to be attained, with the benefit of prolonged use of the catalyst, thereby significantly increasing the technological and economic indicators for the process as a whole.
Table
Table
Table
Table
Example 9
Synthesis of cobalt dichlorodihydroxydisulfophthalocyanine Catalyst
2.19 Moles of carbamide
0.753 mole of monosodium salt of 4-chlorophthalic acid, 0.482 mole of cobalt chloride (CoCl2'4H20) , 0.0158 mole of ammonium molybdate (Mo04(NH4)-/4H20) , and 1.525 moles of ammonium chloride (NH4C1) are thoroughly mixed in a suitable vessel and then heated up to 220-230°C and maintained at constant mixing for 25-30 minutes. The resulting mixture is then ground in a ball mill.
1.31 Moles of oleum and 0.021 mole of boric acid are poured into the ground mixture at 113°C and thoroughly mixed for 90 minutes. The resulting mixture is cooled to 20°C, and then nitrosyl sulfuric acid (NaN02 + H2S04Η20 •= 0.033 mole + 0.56 mole) is added to it. The mixture is maintained at constant mixing for 2 hours.
Water is then added to the obtained mass, which is maintained at 20-25°C for 1 hour. Sodium chloride solution is then poured into the obtained mass, and the mass is mixed for 5 minutes and settled for 4 hours.
After settlement, the upper aqueous layer is poured off, and the precipitate is filtered on a Nutch filter. The obtained paste is dried at 100°C to a residual humidity of no more than 2%. The dried product is ground in a mill, producing the catalyst powder. It should be noted that this powder may contain impurities, but they do not appear to affect the performance of the catalyst.
Claims
01 WHAT IS CLAIMED IS: 02
03 1. A method of extraction of low molecular weight
04 mercaptans from petroleum or gas condensate containing
05 such low molecular weight mercaptans comprising (1)
06 contacting the mercaptans with oxygen in an aqueous
07 solution of a metal hydroxide, in the presence of a
08 cobalt dihalodihydroxy-disulfophthalocyanine catalyst,
09 the catalyst being used in an amount within the range
10 of from about 0.5 x 10'5 to about
2.5 x 10'5 weight
11 percent based on the weight of the petroleum or gas
12 condensate, the catalyst being introduced into the
13 petroleum or gas condensate continuously in the form of
14 a catalytic complex in an aqueous solution of a metal
15 hydroxide, the extraction method being conducted at a
16 temperature ranging from about 40 to about 60°C and a
17 pressure ranging from about 1.0 to about 1.4 MPa, and
18 (2) separating the petroleum or gas condensate from the
19 aqueous solution of metal hydroxide. 20
■21 2. The method of Claim 1 wherein the aqueous solution of a 2 metal hydroxide comprises from about 2 to about 20
23 weight percent metal hydroxide, based on the combined
24 weight of metal hydroxide and water. 25
26 3. The method of Claim 2 wherein the aqueous solution
27 comprises about 20 weight percent metal hydroxide.
28 4. The method of Claim 1 wherein the metal hydroxide is -■9 selected from the group consisting of alkali metal
30 hydroxides and alkaline earth metal hydroxides. 31
3 5. The method of Claim 4 wherein the metal hydroxide is an 33 alkali metal hydroxide. 34 6. The method of Claim 5 wherein the alkali metal hydroxide is sodium hydroxide.
7. The method of Claim 1, wherein the catalytic complex has been prepared by dissolving cobalt dihalodihydroxydisulfo-phthalocyanine in an aqueous solution of a metal hydroxide comprising about 1 weight percent metal hydroxide, based on the combined weight of the metal hydroxide and water, with the subsequent adjustment of the concentration of the metal hydroxide upwards to a level of about 2 to about 20 weight percent.
8. The method of Claim 7 wherein the concentration of the metal hydroxide is adjusted upwards to a level of about 20 weight percent.
9. The method of Claim 7 wherein the metal hydroxide is selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
10. The method of Claim 9 wherein the metal hydroxide is an alkali metal hydroxide.
11. The method of Claim 10 wherein the alkali metal hydroxide is sodium hydroxide.
12. The method of Claim 1 wherein the petroleum is whole crude oil.
13. The method of Claim 7 wherein the petroleum is whole crude oil.
14. Cobalt dihalodihydroxydisulfophthalocyanines having the general formula:
where R is -OH, Rj is halogen and R-j is -S03H.
15. The cobalt dihalodihydroxydisulfophthalocyanines of Claim 14 wherein R, is chlorine or bromine.
16. The cobalt dihalodihydroxydisulfophthalocyanines of Claim 15 wherein R, is chlorine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU94029714 | 1994-08-08 | ||
| RU94029714A RU2087521C1 (en) | 1994-08-08 | 1994-08-08 | Method of removing low-molecular mercaptans from petroleum and gas condensate |
| PCT/IB1995/000623 WO1996005271A1 (en) | 1994-08-08 | 1995-07-27 | A method for the extraction of low molecular weight mercaptans from petroleum and gas condensates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0775182A1 true EP0775182A1 (en) | 1997-05-28 |
Family
ID=20159512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95925985A Withdrawn EP0775182A1 (en) | 1994-08-08 | 1995-07-27 | A method for the extraction of low molecular weight mercaptans from petroleum and gas condensates |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0775182A1 (en) |
| AU (1) | AU2990095A (en) |
| CA (1) | CA2196287A1 (en) |
| MX (1) | MX9700934A (en) |
| NO (1) | NO970588L (en) |
| RU (1) | RU2087521C1 (en) |
| WO (1) | WO1996005271A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2120464C1 (en) * | 1997-09-12 | 1998-10-20 | Всероссийский научно-исследовательский институт углеводородного сырья | Method and installation for deodorizing purification of crude oil and gas condensate from hydrogen sulfide and low-molecular mercaptans |
| RU2189340C2 (en) * | 2000-03-28 | 2002-09-20 | ГУП Всероссийский научно-исследовательский институт углеводородного сырья | Method of storage hydrogen sulphide- and/or mercaptan- containing crude oil, oil products and gas condensate in reservoir in inert gas atmosphere |
| RU2252949C1 (en) * | 2004-01-26 | 2005-05-27 | Фахриев Ахматфаиль Магсумович | Method of petroleum refining from hydrogen sulfide |
| RU2458968C1 (en) * | 2011-02-09 | 2012-08-20 | Ооо "Фотохим" | Catalytic composition for demercaptanisation of oil and oil products |
| MD4420C1 (en) * | 2012-06-26 | 2017-02-28 | Оп "Matricon" Ооо | Use of dark heavy oil components as a catalyst in the oxidative purification of hydrocarbonic compositions from hydrogen sulphide and light mercaptans and process for purification of hydrocarbonic compositions |
| RU2656100C2 (en) * | 2016-11-21 | 2018-05-31 | Закрытое акционерное общество "ИВКАЗ" | Catalytic composition for oil and gas condensate demercaptanisation |
| RU2750214C1 (en) * | 2020-10-01 | 2021-06-24 | Общество с ограниченной ответственностью "Синтез" | Catalyst composition for oxidative demercaptanization of oil and oil products |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3352777A (en) * | 1964-12-09 | 1967-11-14 | Universal Oil Prod Co | Oxidation of mercaptans |
| FR2588266B3 (en) * | 1985-10-04 | 1988-01-15 | Inst Francais Du Petrole | IMPROVED PROCESS FOR SOFTENING FIXED-BED OIL CUTS |
| FR2588265B3 (en) * | 1985-10-04 | 1988-01-15 | Inst Francais Du Petrole | PROCESS FOR SOFTENING A HYDROCARBON FEED CONTAINING SULFUR PRODUCTS |
-
1994
- 1994-08-08 RU RU94029714A patent/RU2087521C1/en active
-
1995
- 1995-07-27 CA CA 2196287 patent/CA2196287A1/en not_active Abandoned
- 1995-07-27 MX MX9700934A patent/MX9700934A/en not_active IP Right Cessation
- 1995-07-27 EP EP95925985A patent/EP0775182A1/en not_active Withdrawn
- 1995-07-27 AU AU29900/95A patent/AU2990095A/en not_active Abandoned
- 1995-07-27 WO PCT/IB1995/000623 patent/WO1996005271A1/en not_active Ceased
-
1997
- 1997-02-07 NO NO970588A patent/NO970588L/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9605271A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| RU94029714A (en) | 1996-06-20 |
| NO970588D0 (en) | 1997-02-07 |
| RU2087521C1 (en) | 1997-08-20 |
| AU2990095A (en) | 1996-03-07 |
| NO970588L (en) | 1997-02-07 |
| CA2196287A1 (en) | 1996-02-22 |
| WO1996005271A1 (en) | 1996-02-22 |
| MX9700934A (en) | 1997-04-30 |
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