CA1168590A - Process for the treatment of a hydrocarbon charge by high temperature ultrafiltration - Google Patents
Process for the treatment of a hydrocarbon charge by high temperature ultrafiltrationInfo
- Publication number
- CA1168590A CA1168590A CA000378030A CA378030A CA1168590A CA 1168590 A CA1168590 A CA 1168590A CA 000378030 A CA000378030 A CA 000378030A CA 378030 A CA378030 A CA 378030A CA 1168590 A CA1168590 A CA 1168590A
- Authority
- CA
- Canada
- Prior art keywords
- oil
- column
- barrier
- charge
- temperature
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/06—Working-up used lubricants to recover useful products ; Cleaning by ultrafiltration or osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/22—Cooling or heating elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/22—Cooling or heating elements
- B01D2313/221—Heat exchangers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the treatment of a hydrocarbon charge by high temperature ultra-filtration, said process comprising the steps of circulating said charge in a module comprising at least one mineral ultrafiltration barrier coated with a sensitive mineral layer of at least one metal oxide and of operating at a temperature higher than 100°C. The barrier, which preferably has a ceramic or metallic support, is coated with a sensitive layer selected from the group comprising titanium dioxide, magnesium oxide, aluminium oxide, spinel MgAl2O4, silica. The invention is applicable to the regeneration of a waste oil and to the reduction of the rate of asphaltenes in a hydrocarbon charge.
The present invention relates to a process for the treatment of a hydrocarbon charge by high temperature ultra-filtration, said process comprising the steps of circulating said charge in a module comprising at least one mineral ultrafiltration barrier coated with a sensitive mineral layer of at least one metal oxide and of operating at a temperature higher than 100°C. The barrier, which preferably has a ceramic or metallic support, is coated with a sensitive layer selected from the group comprising titanium dioxide, magnesium oxide, aluminium oxide, spinel MgAl2O4, silica. The invention is applicable to the regeneration of a waste oil and to the reduction of the rate of asphaltenes in a hydrocarbon charge.
Description
~1~859~
The present invention relates to a process for treat-ment of a hydrocarbon charge by high teInperature ultrafiltration "Hydrocarbon charge" is understood to rnean a charge cornposed mainly of hydrocarbons, but it may also contain other compounds which, apart from the carbon and hydrogen atoms, rnay contain heteroatoms such as oxygen, nitrogen, sulfur or vanadium.
Such charges may be const~tuted in particular by pro-ducts obtained when refining crude oil.
Ultrafiltration is a technique of separation by mass transfer through a semi-permeable membrane under the effect of a pressure gradient, the product collected passing through the membrane constituting the ultrafiltrate Consumption of motor oil in France amounts to appro-ximately 550 000 tons per yearJ frorrl which 250 000 tons per year of waste oil are recovered. Only a small part of these 250 000 tons of waske oil is regenerated by a process including an acid treatment for flocculating the carbon particles that it contains.
This process has the drawback of producing acid sludge which must be eliminated.
Z0 Most of the crude oil supplying French refineries is asphaltic and, after distillation under reduced pressure,yields a residue formed by malthenes, resins and asphaltenes This residue may represent up to 20% of certain crude oils. Deasphalting, which consists in reducing the asphaltene content of this residue is usually effected with the aid of a paraffinic solvent which floccu-lates the asphaltenes as well as a variable proportion of resins.
The asphaltenes constitute pitch whilst the malthenes constitute an oil. This process necessitates a considerable consumption of energy to recover the solvent. It Inay be estimated that the resi-dues of distillation to be deasphalted would be of the order of ten million to fifteen million tons per year if an economical process were available to this end.
However, the valorisation or regeneration, by ultra-filtration, of the oil products or residues has found only few con-crete applications as these products are very viscous and difficult to handle at ambient temperature.
1 ~6859~
Processes for the treatment of oil products ~y ultrafiltra-tion using organic membranes are known. According to one example of such a process described in French Patent No. 2 ~63 296 for a "Process for regeneration of used lubricating oil", the oil, after 5 elimii~ation of various components by distillation, is mixed with a solvent such as n-hexane The mixture obtained is then subjected to ultrafiltration through an organic barrier.
As disclosed in this Patent, the processes for treatment by ultrafiltration with the aid of organic membranes impose a 10 dilution with the aid of a solvent, to have low viscosity, as the or-ganic membranes cannot be used at high temperature. Thus9 in the example cited, the ultrafiltration temperature is only 23C.
It is necessary to disti~l the ultrafiltrate then in order to separate the solvent and the valorisable compound, which is a drawbac~.
It is an object of the present invention to propose an economical process for treating hydrocarbon charges.
The invention relates to such a process for treatment of a hydrocarbon charge by high temperature ultrafiltration using a mineral barrier. This process is applied to the regeneration of a 20 used motor oil. It is also applied to the reduction in the asphaltene content in a hydrocarbon charge constituted for example by a resi-due of distillation ulider reduced pressure of the oil.
More precisely, this process is characterised in that the charge is filtered by means of at least one mineral barrier 25 formed by a support coated with a sensitive rnineral layer of at least one metal oxide and in that operation is carried out at a high temperature greater than 100C and preferably between 100 and 350C.
The pressure o ultrafiltration may in particular be bet-30 ween 1 and 20 relative bars.
The speed of circulation of the charge may be between1 and 10 m/s.
The mineral barrier is a barrier with metal or ceramic support, said support being coated with a sensitive layer of at least 35 one metal oxide chosen from the group in~cluding titanium dioxide, magnesium oxide, aluminium oxide, mixed oxides based on alumina, silica. Such barriers are marketed by the firm SFEC (Société
Francaise de Fabrications Catalytiques) under referenc~s UFS 100 A, UFS 150 ~, UFS 200 A, depending on their radius of permeametryO Barriers of a different radius of permeametry 5 may, of course, be used in the process of the invention and the radius may for example be between 50 A and 250 A .
According to the applications envisaged of the proces~
according to the invention, the barriers may be grouped in variable number in ultrafiltration modules. These modules may be dis 10 posed in series, in parallel or in series-l~arallel. The different modules may contain barriers having different radii of permea-metry, for example the first, barriers of radi; of 200 A, the following of 150 A and so on.
According to a first application, the process accor-lS ding to the invention is used for the regeneration of used motoroils. Such oils, coming for example from an oil change of a vehicle, contain frorn 15 to 20% of impurities. Such impurities are for example water, sludge, carbonaceous particles on which the dispersive agents are adsorbed, products of oxidation of oil 20 or petrol, resins and lacquers in solution in the hot oil, in sus-pension in the cold oil, metallic particles and finally machining liquids .
The ultrafiltrate produced by the process of the inven-tion is of good quality. It contains virt~lally no more metals nor 25 additiv~s. By way of example, the rates of ultrafiltration reach 50Q l/day.m2 with 200A barriers for an operating temperature of 200C, a pressure of 5 bars and a concentration factor of 3.
The process of ultrafiltration according to the inven-tion also finds an application to the reduction in the rate of 30 asphaltenes contained in a hydrocarbon charge.
It is known that the residues of distillation under reduced pressure of crude oils, i. e. the heaviest part, is precisely that part which contains the most viscous lubricating fractions which are of greatest value. Now, the majority of crude oils supplying 35 French refineries are asphaltic and yield, after distillatlon under reduced pressure, a residue formed of malthenes, resins and -~ ~6~5~0 ~ .
asphaltenes re?resenting up to 20% of certain crude oils. ~5 lubricatlng oils must not contain asphaltenes, even in traces, they must be deasphalted. The process of ul~rafiltration accor-ding to the invention finds an application to the reduction in the 5 rate of asphaltenes contained in a hydrocarbon charge. The hydrocarbon charge containing asphaltenes is treated by ultra-filtratIon according to the process of the invention. The asphal-tQ~eS are retained by the barriers and, in the ultrafiltrate, their rate is reduced.
I0 The inventipn will be more readi~y unders t ood on reading the following description with reference to the accom-panying drawings, in wh~ch:
Fig. 1 schematically shows an embodiment of the process of ultrafiltration of the invention.
Fig. 2 ~chematically shows the filtratlon barriers used ln the process of the invention.
Figs. 3 and 4 show embodiments of the process accor-ding to the invention applied to the regeneration of a waste oil.
Referring now to the drawings, Fig.l schematically 20 shows an embodiment of the process according to the invention.
The ultrafiltration module 1 comprises a plurality of mineral barriers for ultrafiltration, but only one barrier has been shown to simplify the drawing. Each barrier is formed by a cylindri-cal ceramic support with an internal diameter of 15 mm and a 25 length of 800 rnm internally coated with an ultrafiltration layer based on metal oxides. The normal direction of flow o ultra-filtrate is therefore from the inside of the barrier to the outside.
- The active surface of each barrier is 360 cm2.
The installation comprises a vat 3 into which is intro-30 duced the charge 4 of hyarocarbon to be treated. The vat 3 isconnected via a pipe 5 to a buffer vat 7. From the buffer vat 7, the charge of ultrafiltrate is introduced under pressure by means of a gear pump 11 inside the ultrafiltration module l. The charge ~
35 c~rculates in ~e ~dule 1. PaIt of this charge fk~s thn~ugh ult~afiltra-tion barriers:this is the ult~afilt~ate.It is collec~ed at 13. The o~er p~rt 6859~
leaves at 15 from the ultrafiltration module 1 to be recycled via a pipe 17 towards the buffer vat 7.
The ultrafiltration barriers are-characterised by their radius of permeametry. These barriers are available on the mar-ket for radii of permeametry of 100, 150 and 200 A
Impurities are present, either in suspension or in solu-tion in the charge 4 of hydrocarbon. These impurities may be constituted for example by sludge, carbonaceous particles, pro-ducts of oxidation of oil or petrol, metal particles, additives in a more or le.ss degraded state. In the course of ultrafiltration, ghese impurities are for the most part retained by the ultrafiltra-tion barriers. Consequently, their concentration incr~ases. The circuit comprises a valve 18 for drawing off the concentrate which enables the level in the buffer vat 7 to be regulated The circuit further comprises a valve 19 for regulating pres sure.
The whole circuit is heat-insulated and laid out electrically. It further comprises apparatus for measuring rate of flow and pressure.
The process for treatment of a hydrocarbon charge, by ultrafiltration, according to the invention, finds application in the regeneration of a waste oil. The hydrocarbon charge 4 is then constituted by the waste oil itself. The different impurities present in this waste oil are retained by the ultrafiltration barriers The ultrafiltrate collected at 13 is constituted by an oil from which its impurities have been removed and of which the characteristics are consequently similar to those of a base oil.
According to the invention, the quality of separation i5 improved by subjecting the waste oils to a heat treatment, which consists in a prior heating of the oil to a temperature of between 200 and 350C
In order to prevent the barriers from progressively clogging, a counter-pressure of ultrafiltrate may periodically be applied on their outer face, and the pressure on the inner face is reduced, this provoking a rsversal of the direction of ultrafiltra-tion. The pressure applied on the outer face may be between l and " 11685gO
30 relative bars. This operation, which is of short duration and -effected at fixed intervals of time, is carried out without interrup-ting the circulation of the hydrocarbon charge inside the barriers and without modiying the temperature.
Fig. 2 shows a diagram o~ an ultrailtration ba~rier used for the regeneration of awaste oil. This barrier is in the form of a tube 21 of 80 cm length, 1. 5 c~n inner diameter, 1. 9 crn outer dianneter. The thickness o the tube 21 is essentially formed by a support rnaterial whose pore radius is of the order of 1~ . The insice o the tube 21 is coated with a sensitive layer 23 whose pores are calibrated as a function of the elements to be separated. The ultrafiltration module comprises 7 barriers placed in a tube 25 of 7. 5 cm diameter~
A connecting cone 27 connects the tube 25 to the pipe 9.
The waste oil penetrates in the ultrailtration ~nodule via the pipe 9s then circulates inside the - high pressure chamber 31. It then 10ws through the barrier 21 towards the low pressure chamber 33.
With a view to allowing tightness between the h;gh pres-sure chamber 31 and low pressure chalnber 33 at the position of the barrier supports, ~the tubes are vitrified at their end over a length o 2 cent imeters. The high pressure and low pressure chambers are isolated by seals 35. These seals 35 are 0-rings made of Viton(~if the temperature is lower than 180C and flat seals treated z5 with graphite i~ the temperature is greater than 180C;.
Figs 3 and 4 show embodiments o the process according to the invention applied to the regeneration o a waste oil. The charge of waste oil is introduced via line 51 into a charrlber 52 where, due to a coil 53 in which a heat transer 1uid circulates, 30 the oil is heated beore being subjected to centrifugation in a cen-trifuge 55 to which it is conducted via line 54 on leaving tl~e cham-ber 52.
The temperature to which the oil is heated in chamber 52 and thereore that at which centriugation is effected, may for 35 example be between 60 and 95~C and in particular close to 90C.
Centrifugation makes it possible to separate the greater l~
, 1685~
part of the water ~nd the solid matters contained in the oil, which are evacuated via line 56. The oil leaving the centrifuge via line S7 passes into an oven 58 where it- is heated before being subjected to a distillation under a pressure close to atmospher;c pressure in a 5 distillation column 60, in the median part of which it is conducted via line 59.
The te-mperature to which the oil is heated in the oven 58, and therefore that at which distillation is effected, may for example be between 150 and 200~C and in particular close to 180C.
A gaseous effluent constituted by light products, such as water not separated in the centrifuge 55, petrol and the chlorinated solvents contained in the oil, is collected at the top of the column 60 via line 61.
The oil is collected at the bottom of the column 601 via 15 line 62. lt is conducted in the median part of a distillation column 63 where the temperature is close to 360C.
The pressure inside the column 63 is equal to or close to atmospheric prçssure.
A fraction constituted by gas oil is collected at the top 20 Of column 63 via line 64.
The oil is collected at the bottom of column 63, via line 65. Part of the oil collected via line 65 is conducted via line 66 in an oven 67 where it is heated to distillation temperature, before being mixed with the charge of line 62 and recycled to column 63.
25 It is oven 67 which supplies calories inside the column 63.
The distillation conducted in colurnn 63 therefore enables the gas oil to be separated frorn the oil. However, at the same time, the oil undergo~s a thermal shock due to the high temperature of oven 67. The effect of this ther~nal shock is to ~reak the moleeules of 30 ~a:aitives contained in the cha~ge and to allow separation of the hèavy m~tals d~ring the subsequent treatments of the oil otiained in line 65.
~ second part of the oil of line 6S is conducted, via line 68, in a centrifuge 69, functioning at a temperature close to 180C.
Centrifugation allows separation of a sludge containing the heavy 35 metals in particular and which is eliminated via line 70.
The oil leaving the centrifuge via line 71 is regenerated -`` 11685~
to be used as base for lubricating oil.
In a conventional process for'regeneration of w~ste oils, the oil leaving the centrifuge via line 71 undergoes an acid treatment to flocculate the carbon particles and sulfonate the 5 oxidised products.
In the process according to the invention, the acid treatment is replaced by an ultrafiltration, which avoids eli~
mination of the acid sludge, In the embodiment shown in Fig. 3, the oil leaving 10 the centrifuge 69 is conducted via line 71 into an ultrafiltration unit 1. ~ heat exchanger may be placed between the centrifuge 69 and the unit 1 to cool or heat the oil to the temperature at which it is desired that ultrafiltration be effected. The non-filtered oil is recycled in the oven 67 via line 72.
The ultrafiltrate is then introduced via line 73 into the median part of a column 85 for distillation under reduced pressure . Fractionsof oil of different viscosities may therefore be collected at different heights of this column via lines 86, which are then subjected to a treatment of catalytic hydrogena-tion to decolorize them. They are introduced into the buffer vats 87 then into the hydrogenation reactor 88. The hydrogen is conducted via line 89. The ,regenerated oil is collected at 90.
In the other embodiment shown in Fig. 4, the distilla-tion carried out in column 631 is effected under reduced pressure.
Different fractions are collected at different heights of the column via lines 64', 65' and 75, which are treated differently.
Gas oil is collected via line 64' at the top of the colurnn. Oil is collected at the bottom of the column via line 65~, of which part is conducted via line 66' into the oven 67' and recycled to column 63'.
The other part of the oil is conducted in the centrifuge 691.
The oil fractions collected via lines 75 at different heights of the column and the one collected via line 71l at the outlet of the centrifuge 6~r, are collected in buffer vats 87, 35 then sequentially ultrafiltered in the unit 1. The non-filtered oil is recycled via line 80 into the over~ 67' ~ 168~9~
_9_ The ultrafiltrate is hydrogenated in the reactor 88 in the same way as in the embodiment of Fig. 3~
The invention is illustrated in non-limiting manner by the following two examples which concern tests made in the installation shown in Figs l and Z
~e~
This example concerns a test of ultrafiltration of a charge of waste oil. This test was carried out at a temperature of 200C with an ultrafiltration module comprising 7 barriers coated with a sensitive layer constituted by mixed oxide of alu-mini~n and of magnesium mixed with silica, with a p~re radius cf 200A. The pressure ~as S relative bars, with a linear speed in the barriers of 3r 23 m/s~ Under these conditions, the rate of ultrafiltration obtained was 6501/d/m2.
The characteristics of the charge of the ultrafiltrate and of the concentrate are given in Table I below.
This example clearly shows the efficiency of the pro-cess according to the invention for regenerating the waste oils.
Example 2 This example co~cerns a test of ultrafiltration of resiaues of distillation in vacuo of a crude oil originating from Kirkuk, Iraq. This test was carried out at a temperature of 330C on an ultrafiltration module comprising 3 barriers coated with a sensitive layer of tltanium dioxide and aluminium oxide, 25 with a radius of permeametry of 100 A The pressure of ultr~
filtration was 5 relative bars and the linear speed 5. 6 m/s. The rate of ultrafiltration was 667 1/d/m2 The characteristics of the charge of the ultrafiltrate and of the concentrate are given in Table II below.
This example shows that the rate of asphaltenes of a charge containing same may be reduced by using the process according to the invention~
1 168~90 O ~ ~ `D ~ ~y O`
o U~ O O ~ ~ ~ ~3 h '. _ _ d1 0 0 df O
_~ o o o oo o o~ooooo~
V~/ V \/V V~ V
. h ~ ~
~d o t~ `D ~ ~ ~ ~ ~ <~ O ~ O
O ~ ~ O ~D
V ~ ~ o ~ o o ~ o ~ o~
¢
O Z; ~ `~
o ~ o O v~ a ~ a 0 0 0 ¢ ¢ ¢ ¢ ~ ~ ~
o , ¢
/~
1 l B ~ O
..
~ U~ V V \~
~ , a) .~
. ~ o ~ ~ ~ ~ CO ~ ~ U~ ~ o o V ~,~, ~ `,`, V~
~G
o ~ , ,~, ~ ~ a` O
~ ~, V V/
¢
, ,~ ¢ ~ ¢ ~ ~ ~ U~
~ ,bl~ ,~
~, ¢
. .
~ 1~859~
TABL~ II
UltrafiltrateCc~ncentrate ~harge asphaltenes (% weight) 4.14 9. 36 6, 30 Vanadium (ppm weight) 90 195 128 density at 15C 0. 98311, 04001, 0156 viscosity at lOODC (cSt) 188 - . 650
The present invention relates to a process for treat-ment of a hydrocarbon charge by high teInperature ultrafiltration "Hydrocarbon charge" is understood to rnean a charge cornposed mainly of hydrocarbons, but it may also contain other compounds which, apart from the carbon and hydrogen atoms, rnay contain heteroatoms such as oxygen, nitrogen, sulfur or vanadium.
Such charges may be const~tuted in particular by pro-ducts obtained when refining crude oil.
Ultrafiltration is a technique of separation by mass transfer through a semi-permeable membrane under the effect of a pressure gradient, the product collected passing through the membrane constituting the ultrafiltrate Consumption of motor oil in France amounts to appro-ximately 550 000 tons per yearJ frorrl which 250 000 tons per year of waste oil are recovered. Only a small part of these 250 000 tons of waske oil is regenerated by a process including an acid treatment for flocculating the carbon particles that it contains.
This process has the drawback of producing acid sludge which must be eliminated.
Z0 Most of the crude oil supplying French refineries is asphaltic and, after distillation under reduced pressure,yields a residue formed by malthenes, resins and asphaltenes This residue may represent up to 20% of certain crude oils. Deasphalting, which consists in reducing the asphaltene content of this residue is usually effected with the aid of a paraffinic solvent which floccu-lates the asphaltenes as well as a variable proportion of resins.
The asphaltenes constitute pitch whilst the malthenes constitute an oil. This process necessitates a considerable consumption of energy to recover the solvent. It Inay be estimated that the resi-dues of distillation to be deasphalted would be of the order of ten million to fifteen million tons per year if an economical process were available to this end.
However, the valorisation or regeneration, by ultra-filtration, of the oil products or residues has found only few con-crete applications as these products are very viscous and difficult to handle at ambient temperature.
1 ~6859~
Processes for the treatment of oil products ~y ultrafiltra-tion using organic membranes are known. According to one example of such a process described in French Patent No. 2 ~63 296 for a "Process for regeneration of used lubricating oil", the oil, after 5 elimii~ation of various components by distillation, is mixed with a solvent such as n-hexane The mixture obtained is then subjected to ultrafiltration through an organic barrier.
As disclosed in this Patent, the processes for treatment by ultrafiltration with the aid of organic membranes impose a 10 dilution with the aid of a solvent, to have low viscosity, as the or-ganic membranes cannot be used at high temperature. Thus9 in the example cited, the ultrafiltration temperature is only 23C.
It is necessary to disti~l the ultrafiltrate then in order to separate the solvent and the valorisable compound, which is a drawbac~.
It is an object of the present invention to propose an economical process for treating hydrocarbon charges.
The invention relates to such a process for treatment of a hydrocarbon charge by high temperature ultrafiltration using a mineral barrier. This process is applied to the regeneration of a 20 used motor oil. It is also applied to the reduction in the asphaltene content in a hydrocarbon charge constituted for example by a resi-due of distillation ulider reduced pressure of the oil.
More precisely, this process is characterised in that the charge is filtered by means of at least one mineral barrier 25 formed by a support coated with a sensitive rnineral layer of at least one metal oxide and in that operation is carried out at a high temperature greater than 100C and preferably between 100 and 350C.
The pressure o ultrafiltration may in particular be bet-30 ween 1 and 20 relative bars.
The speed of circulation of the charge may be between1 and 10 m/s.
The mineral barrier is a barrier with metal or ceramic support, said support being coated with a sensitive layer of at least 35 one metal oxide chosen from the group in~cluding titanium dioxide, magnesium oxide, aluminium oxide, mixed oxides based on alumina, silica. Such barriers are marketed by the firm SFEC (Société
Francaise de Fabrications Catalytiques) under referenc~s UFS 100 A, UFS 150 ~, UFS 200 A, depending on their radius of permeametryO Barriers of a different radius of permeametry 5 may, of course, be used in the process of the invention and the radius may for example be between 50 A and 250 A .
According to the applications envisaged of the proces~
according to the invention, the barriers may be grouped in variable number in ultrafiltration modules. These modules may be dis 10 posed in series, in parallel or in series-l~arallel. The different modules may contain barriers having different radii of permea-metry, for example the first, barriers of radi; of 200 A, the following of 150 A and so on.
According to a first application, the process accor-lS ding to the invention is used for the regeneration of used motoroils. Such oils, coming for example from an oil change of a vehicle, contain frorn 15 to 20% of impurities. Such impurities are for example water, sludge, carbonaceous particles on which the dispersive agents are adsorbed, products of oxidation of oil 20 or petrol, resins and lacquers in solution in the hot oil, in sus-pension in the cold oil, metallic particles and finally machining liquids .
The ultrafiltrate produced by the process of the inven-tion is of good quality. It contains virt~lally no more metals nor 25 additiv~s. By way of example, the rates of ultrafiltration reach 50Q l/day.m2 with 200A barriers for an operating temperature of 200C, a pressure of 5 bars and a concentration factor of 3.
The process of ultrafiltration according to the inven-tion also finds an application to the reduction in the rate of 30 asphaltenes contained in a hydrocarbon charge.
It is known that the residues of distillation under reduced pressure of crude oils, i. e. the heaviest part, is precisely that part which contains the most viscous lubricating fractions which are of greatest value. Now, the majority of crude oils supplying 35 French refineries are asphaltic and yield, after distillatlon under reduced pressure, a residue formed of malthenes, resins and -~ ~6~5~0 ~ .
asphaltenes re?resenting up to 20% of certain crude oils. ~5 lubricatlng oils must not contain asphaltenes, even in traces, they must be deasphalted. The process of ul~rafiltration accor-ding to the invention finds an application to the reduction in the 5 rate of asphaltenes contained in a hydrocarbon charge. The hydrocarbon charge containing asphaltenes is treated by ultra-filtratIon according to the process of the invention. The asphal-tQ~eS are retained by the barriers and, in the ultrafiltrate, their rate is reduced.
I0 The inventipn will be more readi~y unders t ood on reading the following description with reference to the accom-panying drawings, in wh~ch:
Fig. 1 schematically shows an embodiment of the process of ultrafiltration of the invention.
Fig. 2 ~chematically shows the filtratlon barriers used ln the process of the invention.
Figs. 3 and 4 show embodiments of the process accor-ding to the invention applied to the regeneration of a waste oil.
Referring now to the drawings, Fig.l schematically 20 shows an embodiment of the process according to the invention.
The ultrafiltration module 1 comprises a plurality of mineral barriers for ultrafiltration, but only one barrier has been shown to simplify the drawing. Each barrier is formed by a cylindri-cal ceramic support with an internal diameter of 15 mm and a 25 length of 800 rnm internally coated with an ultrafiltration layer based on metal oxides. The normal direction of flow o ultra-filtrate is therefore from the inside of the barrier to the outside.
- The active surface of each barrier is 360 cm2.
The installation comprises a vat 3 into which is intro-30 duced the charge 4 of hyarocarbon to be treated. The vat 3 isconnected via a pipe 5 to a buffer vat 7. From the buffer vat 7, the charge of ultrafiltrate is introduced under pressure by means of a gear pump 11 inside the ultrafiltration module l. The charge ~
35 c~rculates in ~e ~dule 1. PaIt of this charge fk~s thn~ugh ult~afiltra-tion barriers:this is the ult~afilt~ate.It is collec~ed at 13. The o~er p~rt 6859~
leaves at 15 from the ultrafiltration module 1 to be recycled via a pipe 17 towards the buffer vat 7.
The ultrafiltration barriers are-characterised by their radius of permeametry. These barriers are available on the mar-ket for radii of permeametry of 100, 150 and 200 A
Impurities are present, either in suspension or in solu-tion in the charge 4 of hydrocarbon. These impurities may be constituted for example by sludge, carbonaceous particles, pro-ducts of oxidation of oil or petrol, metal particles, additives in a more or le.ss degraded state. In the course of ultrafiltration, ghese impurities are for the most part retained by the ultrafiltra-tion barriers. Consequently, their concentration incr~ases. The circuit comprises a valve 18 for drawing off the concentrate which enables the level in the buffer vat 7 to be regulated The circuit further comprises a valve 19 for regulating pres sure.
The whole circuit is heat-insulated and laid out electrically. It further comprises apparatus for measuring rate of flow and pressure.
The process for treatment of a hydrocarbon charge, by ultrafiltration, according to the invention, finds application in the regeneration of a waste oil. The hydrocarbon charge 4 is then constituted by the waste oil itself. The different impurities present in this waste oil are retained by the ultrafiltration barriers The ultrafiltrate collected at 13 is constituted by an oil from which its impurities have been removed and of which the characteristics are consequently similar to those of a base oil.
According to the invention, the quality of separation i5 improved by subjecting the waste oils to a heat treatment, which consists in a prior heating of the oil to a temperature of between 200 and 350C
In order to prevent the barriers from progressively clogging, a counter-pressure of ultrafiltrate may periodically be applied on their outer face, and the pressure on the inner face is reduced, this provoking a rsversal of the direction of ultrafiltra-tion. The pressure applied on the outer face may be between l and " 11685gO
30 relative bars. This operation, which is of short duration and -effected at fixed intervals of time, is carried out without interrup-ting the circulation of the hydrocarbon charge inside the barriers and without modiying the temperature.
Fig. 2 shows a diagram o~ an ultrailtration ba~rier used for the regeneration of awaste oil. This barrier is in the form of a tube 21 of 80 cm length, 1. 5 c~n inner diameter, 1. 9 crn outer dianneter. The thickness o the tube 21 is essentially formed by a support rnaterial whose pore radius is of the order of 1~ . The insice o the tube 21 is coated with a sensitive layer 23 whose pores are calibrated as a function of the elements to be separated. The ultrafiltration module comprises 7 barriers placed in a tube 25 of 7. 5 cm diameter~
A connecting cone 27 connects the tube 25 to the pipe 9.
The waste oil penetrates in the ultrailtration ~nodule via the pipe 9s then circulates inside the - high pressure chamber 31. It then 10ws through the barrier 21 towards the low pressure chamber 33.
With a view to allowing tightness between the h;gh pres-sure chamber 31 and low pressure chalnber 33 at the position of the barrier supports, ~the tubes are vitrified at their end over a length o 2 cent imeters. The high pressure and low pressure chambers are isolated by seals 35. These seals 35 are 0-rings made of Viton(~if the temperature is lower than 180C and flat seals treated z5 with graphite i~ the temperature is greater than 180C;.
Figs 3 and 4 show embodiments o the process according to the invention applied to the regeneration o a waste oil. The charge of waste oil is introduced via line 51 into a charrlber 52 where, due to a coil 53 in which a heat transer 1uid circulates, 30 the oil is heated beore being subjected to centrifugation in a cen-trifuge 55 to which it is conducted via line 54 on leaving tl~e cham-ber 52.
The temperature to which the oil is heated in chamber 52 and thereore that at which centriugation is effected, may for 35 example be between 60 and 95~C and in particular close to 90C.
Centrifugation makes it possible to separate the greater l~
, 1685~
part of the water ~nd the solid matters contained in the oil, which are evacuated via line 56. The oil leaving the centrifuge via line S7 passes into an oven 58 where it- is heated before being subjected to a distillation under a pressure close to atmospher;c pressure in a 5 distillation column 60, in the median part of which it is conducted via line 59.
The te-mperature to which the oil is heated in the oven 58, and therefore that at which distillation is effected, may for example be between 150 and 200~C and in particular close to 180C.
A gaseous effluent constituted by light products, such as water not separated in the centrifuge 55, petrol and the chlorinated solvents contained in the oil, is collected at the top of the column 60 via line 61.
The oil is collected at the bottom of the column 601 via 15 line 62. lt is conducted in the median part of a distillation column 63 where the temperature is close to 360C.
The pressure inside the column 63 is equal to or close to atmospheric prçssure.
A fraction constituted by gas oil is collected at the top 20 Of column 63 via line 64.
The oil is collected at the bottom of column 63, via line 65. Part of the oil collected via line 65 is conducted via line 66 in an oven 67 where it is heated to distillation temperature, before being mixed with the charge of line 62 and recycled to column 63.
25 It is oven 67 which supplies calories inside the column 63.
The distillation conducted in colurnn 63 therefore enables the gas oil to be separated frorn the oil. However, at the same time, the oil undergo~s a thermal shock due to the high temperature of oven 67. The effect of this ther~nal shock is to ~reak the moleeules of 30 ~a:aitives contained in the cha~ge and to allow separation of the hèavy m~tals d~ring the subsequent treatments of the oil otiained in line 65.
~ second part of the oil of line 6S is conducted, via line 68, in a centrifuge 69, functioning at a temperature close to 180C.
Centrifugation allows separation of a sludge containing the heavy 35 metals in particular and which is eliminated via line 70.
The oil leaving the centrifuge via line 71 is regenerated -`` 11685~
to be used as base for lubricating oil.
In a conventional process for'regeneration of w~ste oils, the oil leaving the centrifuge via line 71 undergoes an acid treatment to flocculate the carbon particles and sulfonate the 5 oxidised products.
In the process according to the invention, the acid treatment is replaced by an ultrafiltration, which avoids eli~
mination of the acid sludge, In the embodiment shown in Fig. 3, the oil leaving 10 the centrifuge 69 is conducted via line 71 into an ultrafiltration unit 1. ~ heat exchanger may be placed between the centrifuge 69 and the unit 1 to cool or heat the oil to the temperature at which it is desired that ultrafiltration be effected. The non-filtered oil is recycled in the oven 67 via line 72.
The ultrafiltrate is then introduced via line 73 into the median part of a column 85 for distillation under reduced pressure . Fractionsof oil of different viscosities may therefore be collected at different heights of this column via lines 86, which are then subjected to a treatment of catalytic hydrogena-tion to decolorize them. They are introduced into the buffer vats 87 then into the hydrogenation reactor 88. The hydrogen is conducted via line 89. The ,regenerated oil is collected at 90.
In the other embodiment shown in Fig. 4, the distilla-tion carried out in column 631 is effected under reduced pressure.
Different fractions are collected at different heights of the column via lines 64', 65' and 75, which are treated differently.
Gas oil is collected via line 64' at the top of the colurnn. Oil is collected at the bottom of the column via line 65~, of which part is conducted via line 66' into the oven 67' and recycled to column 63'.
The other part of the oil is conducted in the centrifuge 691.
The oil fractions collected via lines 75 at different heights of the column and the one collected via line 71l at the outlet of the centrifuge 6~r, are collected in buffer vats 87, 35 then sequentially ultrafiltered in the unit 1. The non-filtered oil is recycled via line 80 into the over~ 67' ~ 168~9~
_9_ The ultrafiltrate is hydrogenated in the reactor 88 in the same way as in the embodiment of Fig. 3~
The invention is illustrated in non-limiting manner by the following two examples which concern tests made in the installation shown in Figs l and Z
~e~
This example concerns a test of ultrafiltration of a charge of waste oil. This test was carried out at a temperature of 200C with an ultrafiltration module comprising 7 barriers coated with a sensitive layer constituted by mixed oxide of alu-mini~n and of magnesium mixed with silica, with a p~re radius cf 200A. The pressure ~as S relative bars, with a linear speed in the barriers of 3r 23 m/s~ Under these conditions, the rate of ultrafiltration obtained was 6501/d/m2.
The characteristics of the charge of the ultrafiltrate and of the concentrate are given in Table I below.
This example clearly shows the efficiency of the pro-cess according to the invention for regenerating the waste oils.
Example 2 This example co~cerns a test of ultrafiltration of resiaues of distillation in vacuo of a crude oil originating from Kirkuk, Iraq. This test was carried out at a temperature of 330C on an ultrafiltration module comprising 3 barriers coated with a sensitive layer of tltanium dioxide and aluminium oxide, 25 with a radius of permeametry of 100 A The pressure of ultr~
filtration was 5 relative bars and the linear speed 5. 6 m/s. The rate of ultrafiltration was 667 1/d/m2 The characteristics of the charge of the ultrafiltrate and of the concentrate are given in Table II below.
This example shows that the rate of asphaltenes of a charge containing same may be reduced by using the process according to the invention~
1 168~90 O ~ ~ `D ~ ~y O`
o U~ O O ~ ~ ~ ~3 h '. _ _ d1 0 0 df O
_~ o o o oo o o~ooooo~
V~/ V \/V V~ V
. h ~ ~
~d o t~ `D ~ ~ ~ ~ ~ <~ O ~ O
O ~ ~ O ~D
V ~ ~ o ~ o o ~ o ~ o~
¢
O Z; ~ `~
o ~ o O v~ a ~ a 0 0 0 ¢ ¢ ¢ ¢ ~ ~ ~
o , ¢
/~
1 l B ~ O
..
~ U~ V V \~
~ , a) .~
. ~ o ~ ~ ~ ~ CO ~ ~ U~ ~ o o V ~,~, ~ `,`, V~
~G
o ~ , ,~, ~ ~ a` O
~ ~, V V/
¢
, ,~ ¢ ~ ¢ ~ ~ ~ U~
~ ,bl~ ,~
~, ¢
. .
~ 1~859~
TABL~ II
UltrafiltrateCc~ncentrate ~harge asphaltenes (% weight) 4.14 9. 36 6, 30 Vanadium (ppm weight) 90 195 128 density at 15C 0. 98311, 04001, 0156 viscosity at lOODC (cSt) 188 - . 650
Claims (14)
1. A process for the treatment of a liquid hydrocarbon charge by ultrafiltration to remove unwanted impurities from said liquid hydrocarbon, said process consisting essentially of circulating said charge at a temperature greater than 100°C in at least one module comprising at least one mineral ultrafiltration barrier coated with a sensitive layer of mixed oxide of mag-nesium and aluminum mixed with silica the direction of said circulation being such that said liquid hydrocarbon charge initially contacts an outer surface of said coating whereby said impurities are removed from said liquid hydrocarbon charge by said coated barrier to produce an ultrafiltrate essentially free of impurities, said barrier having a radius of permeametry between 50.ANG.
and 250.ANG. and being adapted to support a counter pressure of between 1 and 30 relative bars.
and 250.ANG. and being adapted to support a counter pressure of between 1 and 30 relative bars.
2. The process of Claim 1 wherein, without interrupting the circulation of said liquid hydrocarbon charge through said at least one barrier, a counter-pressure of ultrafiltrate is momentarily applied to a non-coated surface of said at least one barrier to pro-voke a reversal of the direction of said circulation.
3. The process of Claim 1, wherein the speed of circulation of said liquid hydrocarbon charge is between 1 and 10 m/s.
4. The process of Claim 1, wherein said treatment is carried out at a temperature of between 100° and 350°C.
5. The process of Claim 1, wherein said liquid hydrocarbon charge contains asphaltenes and said ultrafiltrate contains a lesser concentration of alpha-tenes than said charge.
6. The method of Claim 1, wherein said liquid hydrocarbon charge is waste oil containing water and solid matter and said method includes the steps of:
- heating the waste oil, - centrifuging it in order to separate the water and the solid matter, - heating it in an oven to a temperature of between 150 and 200°C, - distilling it, under a pressure close to atmospheric pressure, in a first column, - collecting the waste oil at the bottom of said first distillation column, - introducing it in the median part of a second distil-lation column in which it is distilled under a pressure close to atmospheric pressure, at a tempera-ture of 360°C, - collecting the oil at the bottom of the second column, - recycling part of the oil collected at the bottom of the second column to an oven where it is heated to a temperature of distillation, before being mixed with the charge of the line from the first column and recycled in the second column, - centrifuging a second part of the oil at a temperature close to 180°C in a centrifuge, and - wherein the oil leaving the centrifuge is filtered in said at least one ultrafiltration module.
- heating the waste oil, - centrifuging it in order to separate the water and the solid matter, - heating it in an oven to a temperature of between 150 and 200°C, - distilling it, under a pressure close to atmospheric pressure, in a first column, - collecting the waste oil at the bottom of said first distillation column, - introducing it in the median part of a second distil-lation column in which it is distilled under a pressure close to atmospheric pressure, at a tempera-ture of 360°C, - collecting the oil at the bottom of the second column, - recycling part of the oil collected at the bottom of the second column to an oven where it is heated to a temperature of distillation, before being mixed with the charge of the line from the first column and recycled in the second column, - centrifuging a second part of the oil at a temperature close to 180°C in a centrifuge, and - wherein the oil leaving the centrifuge is filtered in said at least one ultrafiltration module.
7. The method of Claim 1, wherein said liquid hydrocarbon charge is waste oil containing waste and solid matter and said method includes the steps of:
heating the waste oil, centrifuging it in order to separate the water and the solid matters, - heating it in an oven to a temperature of between 150 and 200°C, - distilling it under a pressure close to atmospheric pressure, in a first column, - collecting the waste oil at the bottom of said first distillation column, - introducing it into the median part of a second distillation column in which it is distilled under a pressure lower than atmospheric pressure, at a temper-ature of 360°C, - collecting:
a) a first oil fraction at the bottom of the second column, -recycling part of the oil collected at the bottom of the second column in an oven where it is heated to the temperature of distillation, before being mixed with the charge if the line from the first column and recycled in the second column, -centrifuging a second part of the oil at a temperature of 180°C in a centrifuge, b) different oil fractions at different heights of the second column, wherein the oil leaving the centrifuge from a) and the different oil fractions of b) are filtered in said ultrafiltration module and then undergo a hydrogenation treatment.
heating the waste oil, centrifuging it in order to separate the water and the solid matters, - heating it in an oven to a temperature of between 150 and 200°C, - distilling it under a pressure close to atmospheric pressure, in a first column, - collecting the waste oil at the bottom of said first distillation column, - introducing it into the median part of a second distillation column in which it is distilled under a pressure lower than atmospheric pressure, at a temper-ature of 360°C, - collecting:
a) a first oil fraction at the bottom of the second column, -recycling part of the oil collected at the bottom of the second column in an oven where it is heated to the temperature of distillation, before being mixed with the charge if the line from the first column and recycled in the second column, -centrifuging a second part of the oil at a temperature of 180°C in a centrifuge, b) different oil fractions at different heights of the second column, wherein the oil leaving the centrifuge from a) and the different oil fractions of b) are filtered in said ultrafiltration module and then undergo a hydrogenation treatment.
8. The process of Claim 1, wherein the mineral barrier is a barrier with a ceramic support.
9. The process of Claim 1, wherein the mineral barrier is a barrier with a metal support.
10. The process of Claim 1, wherein the pressure of ultrafiltration is between 1 and 20 relative bars.
11. The process of Claim 1, applied to the regeneration of a waste oil, wherein the charge is constituted by waste oil, the ultrafiltrate obtained constituting an oil purified of its impurities.
12. The process of Claim 11, wherein the waste oil is subjected to a heat treatment prior to its ultra-filtration, at a temperature of between 200 and 350 C.
13. The process of Claim 5, wherein the radius of the pores of the barrier is 100 .ANG..
14. The process of Claim 6, wherein the ultra-filtrate obtained on leaving the module is distilled at a pressure lower than atmospheric pressure, and oils of different viscosities are collected via lines located at different heights on a third distillation column, which undergo a hydrogenation treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8011442A FR2482975A1 (en) | 1980-05-22 | 1980-05-22 | PROCESS FOR TREATING ULTRAFILTRATION AT HIGH TEMPERATURE OF A HYDROCARBONATED LOAD |
| FR8011442 | 1980-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168590A true CA1168590A (en) | 1984-06-05 |
Family
ID=9242236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000378030A Expired CA1168590A (en) | 1980-05-22 | 1981-05-21 | Process for the treatment of a hydrocarbon charge by high temperature ultrafiltration |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4411790A (en) |
| EP (1) | EP0041013B1 (en) |
| AT (1) | ATE15067T1 (en) |
| CA (1) | CA1168590A (en) |
| DE (1) | DE3171898D1 (en) |
| ES (1) | ES8300841A1 (en) |
| FR (1) | FR2482975A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208079B2 (en) | 2002-07-30 | 2007-04-24 | Nouredine Fakhri | Process for the treatment of waste oils |
| US8652572B2 (en) | 2006-10-11 | 2014-02-18 | The United States Of America As Represented By The Secretary Of The Navy | Method to produce particulate filter |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797200A (en) * | 1984-05-04 | 1989-01-10 | Exxon Research And Engineering Company | Upgrading heavy oils by solvent dissolution and ultrafiltration |
| CA1263845A (en) * | 1985-08-28 | 1989-12-12 | Oleh Kutowy | Method of removing substances from fossil derived, hydrocarbon liquids |
| IL79985A0 (en) * | 1985-09-13 | 1986-12-31 | Ausimont Spa | Purification of oils containing solid matter in suspension |
| FR2587629B1 (en) * | 1985-09-25 | 1993-07-16 | Raffinage Cie Francaise | PROCESS FOR SEPARATION OF FINE CATALYST PARTICLES FROM A HYDROCARBON CHARGE, BY FILTRATION THROUGH MINERAL BARRIERS AND FILTRATION LOOP |
| FR2593079A1 (en) * | 1986-01-20 | 1987-07-24 | Total France | Process for separating, by microfiltration, at least one solid phase from a gaseous phase, and use in a process for gasifying a hydrocarbon feedstock |
| FR2594137B1 (en) * | 1986-02-10 | 1989-02-17 | Inst Francais Du Petrole | PROCESS FOR HYDROTREATING LIQUID PHASE HEAVY HYDROCARBONS IN THE PRESENCE OF A DISPERSE CATALYST |
| FR2596766B1 (en) * | 1986-04-02 | 1988-05-20 | Inst Francais Du Petrole | PROCESS FOR DEASPHALTING A HYDROCARBON OIL |
| FR2598717B1 (en) * | 1986-05-14 | 1988-08-26 | Inst Francais Du Petrole | PROCESS FOR DEASPHALTING A HYDROCARBON OIL CONTAINING ASPHALT |
| US4692251A (en) * | 1986-07-07 | 1987-09-08 | Hilgren Wallace L | Solvent cleansing apparatus |
| GB8617592D0 (en) * | 1986-07-18 | 1986-08-28 | Shell Int Research | Separating fluid mixture |
| GB8619278D0 (en) * | 1986-08-07 | 1986-09-17 | Shell Int Research | Separating fluid feed mixture |
| US4759850A (en) * | 1987-01-12 | 1988-07-26 | Energy, Mines And Resources Canada | Membrane process for separating methanol from methanol/hydrocarbon solutions |
| FR2628749B1 (en) * | 1988-03-17 | 1993-10-22 | Cgee Alsthom | PROCESS FOR THE TREATMENT OF POLLUTED WATER EMULSIONS OR MICROEMULSIONS |
| ES2034291T3 (en) * | 1988-03-17 | 1993-04-01 | Societe Des Ceramiques Techniques | PROCEDURE FOR THE TREATMENT OF EMULSIONS OR MICROEMULSIONS OF OIL IN CONTAMINATED WATER. |
| US4962271A (en) * | 1989-12-19 | 1990-10-09 | Exxon Research And Engineering Company | Selective separation of multi-ring aromatic hydrocarbons from distillates by perstraction |
| US5173172A (en) * | 1991-08-19 | 1992-12-22 | Exxon Research And Engineering Company | Production of hard asphalts by ultrafiltration of vacuum residua |
| US5256297A (en) * | 1992-12-17 | 1993-10-26 | Exxon Research And Engineering Company | Multi-stage ultrafiltration process (OP-3711) |
| US5276244A (en) * | 1993-03-30 | 1994-01-04 | Ethyl Corporation | Separation of aluminum alkyls from olefins using modified inorganic membranes |
| WO1995008609A1 (en) * | 1993-09-22 | 1995-03-30 | Amore Piero D | Microfiltration of used oil |
| US5534133A (en) * | 1994-11-17 | 1996-07-09 | Ucar Carbon Technology Corporation | Continuous method for increasing the Q. I. concentration of liquid tar while concurrently producing a Q. I. free tar |
| US6013174A (en) * | 1996-02-21 | 2000-01-11 | U.S. Filter Recovery Services (Mid-Atlantic, Inc.) | Process to remove ash-forming contaminants from used oil |
| US6024880A (en) * | 1996-02-26 | 2000-02-15 | Ciora, Jr.; Richard J. | Refining of used oils using membrane- and adsorption-based processes |
| US5785860A (en) * | 1996-09-13 | 1998-07-28 | University Of British Columbia | Upgrading heavy oil by ultrafiltration using ceramic membrane |
| FR2761899B1 (en) | 1997-04-15 | 1999-05-28 | Commissariat Energie Atomique | METHOD AND INSTALLATION FOR TANGENTIAL FILTRATION OF A VISCOUS LIQUID |
| US6117327A (en) * | 1997-08-22 | 2000-09-12 | Media And Process Technology Inc. | Deashing and demetallization of used oil using a membrane process |
| US6090273A (en) * | 1997-12-03 | 2000-07-18 | U.S. Filter Recovery Services (Mid-Altantic, Inc.) | Process to remove ash-forming contaminants from wet used oil |
| CO4810316A1 (en) * | 1998-01-29 | 1999-06-30 | Environmental Safeguards Inc | APPARATUS AND PROCESS FOR THE SEPARATION OF LIQUIDS AND SOLIDS |
| US6524469B1 (en) | 2000-05-16 | 2003-02-25 | Trans Ionics Corporation | Heavy oil upgrading process |
| US20030019790A1 (en) * | 2000-05-16 | 2003-01-30 | Trans Ionics Corporation | Heavy oil upgrading processes |
| US6502635B1 (en) | 2001-06-20 | 2003-01-07 | Chevron U.S.A. Inc. | Sub-sea membrane separation system with temperature control |
| EP1440136A1 (en) * | 2001-10-18 | 2004-07-28 | Shell Internationale Researchmaatschappij B.V. | Continuous process to separate colour bodies and/or asphalthenic contaminants from a hydrocarbon mixture |
| EP1620529B1 (en) * | 2003-04-17 | 2007-07-11 | Shell Internationale Researchmaatschappij B.V. | Process to separate colour bodies and/or asphalthenic contaminants from a hydrocarbon mixture |
| US7763163B2 (en) * | 2006-10-20 | 2010-07-27 | Saudi Arabian Oil Company | Process for removal of nitrogen and poly-nuclear aromatics from hydrocracker feedstocks |
| US9315733B2 (en) * | 2006-10-20 | 2016-04-19 | Saudi Arabian Oil Company | Asphalt production from solvent deasphalting bottoms |
| US8246814B2 (en) * | 2006-10-20 | 2012-08-21 | Saudi Arabian Oil Company | Process for upgrading hydrocarbon feedstocks using solid adsorbent and membrane separation of treated product stream |
| US7566394B2 (en) * | 2006-10-20 | 2009-07-28 | Saudi Arabian Oil Company | Enhanced solvent deasphalting process for heavy hydrocarbon feedstocks utilizing solid adsorbent |
| CN101070507B (en) * | 2007-06-05 | 2010-05-19 | 天津新膜科技有限责任公司 | Regeneration method for waste lubricant and apparatus |
| US7871510B2 (en) * | 2007-08-28 | 2011-01-18 | Exxonmobil Research & Engineering Co. | Production of an enhanced resid coker feed using ultrafiltration |
| US7897828B2 (en) * | 2007-08-28 | 2011-03-01 | Exxonmobile Research And Engineering Company | Process for separating a heavy oil feedstream into improved products |
| US7815790B2 (en) | 2007-08-28 | 2010-10-19 | Exxonmobil Research And Engineering Company | Upgrade of visbroken residua products by ultrafiltration |
| US8864996B2 (en) * | 2007-08-28 | 2014-10-21 | Exxonmobil Research And Engineering Company | Reduction of conradson carbon residue and average boiling points utilizing high pressure ultrafiltration |
| US7867379B2 (en) * | 2007-08-28 | 2011-01-11 | Exxonmobil Research And Engineering Company | Production of an upgraded stream from steam cracker tar by ultrafiltration |
| US8177965B2 (en) * | 2007-08-28 | 2012-05-15 | Exxonmobil Research And Engineering Company | Enhancement of saturates content in heavy hydrocarbons utilizing ultrafiltration |
| US7736493B2 (en) * | 2007-08-28 | 2010-06-15 | Exxonmobil Research And Engineering Company | Deasphalter unit throughput increase via resid membrane feed preparation |
| WO2009082493A1 (en) * | 2007-12-24 | 2009-07-02 | Saudi Arabian Oil Company | Membrane desulfurization of liquid hydrocarbon feedstreams |
| US20110000823A1 (en) * | 2009-07-01 | 2011-01-06 | Feras Hamad | Membrane desulfurization of liquid hydrocarbons using an extractive liquid membrane contactor system and method |
| FR2957353B1 (en) * | 2010-03-10 | 2014-09-05 | Commissariat Energie Atomique | PROCESS FOR REMOVING ONE OR MORE COMPOUNDS FROM A HYDROCARBONATED LOAD |
| WO2011116059A1 (en) * | 2010-03-16 | 2011-09-22 | Saudi Arabian Oil Company | System and process for integrated oxidative desulfurization, desalting and deasphalting of hydrocarbon feedstocks |
| US8790508B2 (en) | 2010-09-29 | 2014-07-29 | Saudi Arabian Oil Company | Integrated deasphalting and oxidative removal of heteroatom hydrocarbon compounds from liquid hydrocarbon feedstocks |
| CN102021016B (en) * | 2010-10-29 | 2014-02-26 | 南京工业大学 | Method for deacidification of alkylation reaction product |
| US8454832B2 (en) | 2010-11-29 | 2013-06-04 | Saudi Arabian Oil Company | Supported ionic liquid membrane system and process for aromatic separation from hydrocarbon feeds |
| CN103827267A (en) | 2011-07-29 | 2014-05-28 | 沙特阿拉伯石油公司 | Process for stabilization of heavy hydrocarbons |
| US10125319B2 (en) | 2011-07-31 | 2018-11-13 | Saudi Arabian Oil Company | Integrated process to produce asphalt and desulfurized oil |
| SG11201700397TA (en) | 2014-07-25 | 2017-02-27 | Saudi Arabian Oil Co | Integrated process to produce asphalt, petroleum green coke, and liquid and gas coking unit products |
| CN107849467B (en) | 2015-07-27 | 2020-10-30 | 沙特阿拉伯石油公司 | Integrated enhanced solvent deasphalting and coking process for producing petroleum green coke |
| WO2023200709A1 (en) * | 2022-04-12 | 2023-10-19 | ExxonMobil Technology and Engineering Company | Methods and systems for treatment of used oils using membranes |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR886208A (en) * | 1942-06-08 | 1943-10-08 | Process for treating old used oils with a view to their regeneration | |
| FR932922A (en) * | 1944-03-24 | 1948-04-06 | Paul De Marne & Cie | Regeneration of used lubricating oils |
| FR924253A (en) * | 1945-03-21 | 1947-07-31 | Bataafsche Petroleum | Process for regenerating used lubricating oils intended for internal combustion engines |
| FR1197982A (en) * | 1958-01-27 | 1959-12-03 | Commissariat Energie Atomique | Very fine porous porous membranes and their manufacturing process |
| US3947327A (en) * | 1971-07-22 | 1976-03-30 | Hanover Research Corporation | Process and apparatus for recovering clean water from aqueous wastes |
| US3853756A (en) * | 1973-02-12 | 1974-12-10 | Westinghouse Electric Corp | Reverse pressure cleaning of supported semipermeable membranes |
| US3977967A (en) * | 1973-05-10 | 1976-08-31 | Union Carbide Corporation | Ultrafiltration apparatus and process for the treatment of liquids |
| FR2251351A1 (en) * | 1973-11-20 | 1975-06-13 | Commissariat Energie Atomique | Ceramic ultra filter mfr. - by making conductive a macroporous ceramic support and coating with a microporous layer |
| FR2263296B1 (en) * | 1974-03-06 | 1976-12-10 | Inst Francais Du Petrole | |
| US4033859A (en) * | 1975-04-24 | 1977-07-05 | Witco Chemical Corporation | Thermal treatment of used petroleum oils |
| US4060488A (en) * | 1975-11-20 | 1977-11-29 | E. I. Du Pont De Nemours And Company | Particulate membrane ultrafiltration device |
| US4071438A (en) * | 1976-06-03 | 1978-01-31 | Vacsol Corporation | Method of reclaiming waste oil by distillation and extraction |
| CA1107673A (en) * | 1977-05-16 | 1981-08-25 | Gerhard P. Nowack | Reclaiming used lubricating oils |
| US4239616A (en) * | 1979-07-23 | 1980-12-16 | Kerr-Mcgee Refining Corporation | Solvent deasphalting |
-
1980
- 1980-05-22 FR FR8011442A patent/FR2482975A1/en active Granted
-
1981
- 1981-05-20 US US06/265,660 patent/US4411790A/en not_active Expired - Fee Related
- 1981-05-20 DE DE8181400793T patent/DE3171898D1/en not_active Expired
- 1981-05-20 EP EP81400793A patent/EP0041013B1/en not_active Expired
- 1981-05-20 AT AT81400793T patent/ATE15067T1/en not_active IP Right Cessation
- 1981-05-21 CA CA000378030A patent/CA1168590A/en not_active Expired
- 1981-05-22 ES ES502439A patent/ES8300841A1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208079B2 (en) | 2002-07-30 | 2007-04-24 | Nouredine Fakhri | Process for the treatment of waste oils |
| US8652572B2 (en) | 2006-10-11 | 2014-02-18 | The United States Of America As Represented By The Secretary Of The Navy | Method to produce particulate filter |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3171898D1 (en) | 1985-09-26 |
| FR2482975B1 (en) | 1985-05-24 |
| ES502439A0 (en) | 1982-11-01 |
| ATE15067T1 (en) | 1985-09-15 |
| US4411790A (en) | 1983-10-25 |
| ES8300841A1 (en) | 1982-11-01 |
| EP0041013B1 (en) | 1985-08-21 |
| FR2482975A1 (en) | 1981-11-27 |
| EP0041013A1 (en) | 1981-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1168590A (en) | Process for the treatment of a hydrocarbon charge by high temperature ultrafiltration | |
| CN108251156B (en) | Method for two-stage hydrotreating regeneration process of full-fraction waste mineral oil | |
| US5236577A (en) | Process for separation of hydrocarbon from tar sands froth | |
| CN1320080C (en) | Membrane separation for sulfur reduction | |
| US3769200A (en) | Method of producing high purity coke by delayed coking | |
| US4747936A (en) | Deasphalting and demetallizing heavy oils | |
| EP2831202B1 (en) | Process for removing nitrogen from fuel streams with caprolactamium ionic liquids | |
| JP2008533240A (en) | Method for producing lubricating base oil from waste oil | |
| US4756821A (en) | Method for the liquid phase hydrotreatment of heavy hydrocarbons in the presence of a dispersed catalyst | |
| KR20010023757A (en) | Method of re-refining waste oil by distillation and extraction | |
| US5350503A (en) | Method of producing consistent high quality coke | |
| NO162972B (en) | PROCEDURE FOR THE REFINING OF USED LUBRICANTS. | |
| JPH03172388A (en) | Extraction of solvent for lubricant | |
| EP1210401B1 (en) | Method of removing contaminants from petroleum distillates | |
| US4486299A (en) | Removing NH3 and H2 S from aqueous streams | |
| US2685561A (en) | Deashing of reduced crudes by an integrated operation | |
| CA1209512A (en) | Used oil re-refining | |
| US2834715A (en) | Preparation of catalytic cracking feed | |
| US2906694A (en) | Integrated hydrofining process | |
| US3671422A (en) | Water pollution abatement in a petroleum refinery | |
| CA2115518A1 (en) | Hydrotreating process | |
| US4022675A (en) | Filtering process | |
| US5223152A (en) | Recovered oil dewatering process and apparatus with water vaporizing in blowdown drum | |
| US2999808A (en) | Waste water treatment | |
| US4555310A (en) | Method of utilizing energy of high pressure condensate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |