JPH0412760B2 - - Google Patents

Abstract

Regenerated sorbent employed for refining of heavy crude feedstocks is used to remove contaminants from specialized hydrocarbons, especially used motor oil. The simultaneous operation of a decontaminating unit supplied with regenerated sorbent particulate from the regenerator of a heavy hydrocarbon refining system is utilized.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for removing undesirable substances and ash from used or otherwise contaminated motor oil. The present invention avoids the environmental problems associated with disposing of heavy metal salts and other persistent contaminants in used motor oil by transferring it to landfill aquifers, mud ponds, or storage drums that themselves degrade. Also related.

(Prior Art) Regeneration of used motor oil is distinguished from rerefining, and is not the process of high-temperature distillation of motor oil raw materials. That is, the regeneration process typically
It is a cheaper method than re-refining. Although reclamation has value in recovering lubricating oil feedstock, its application has been limited to very few due to the expense of collecting and transporting small amounts of oil condensate to processing centers. However, recent public awareness of the potential for water contamination by used motor oil has generated new incentives for reclamation.

Motor oil reclamation is commonly treated with solvents containing active refining agents. Although a purer motor oil is obtained, a significant amount of sludge is usually produced as a byproduct of contaminated solvent. This sludge must then be disposed of in some non-contaminating manner. Often this sludge is concentrated by relatively expensive flash distillation.

For example, Mattox's U.S. patent no.
No. 4105538 adds a light paraffinic hydrocarbon fraction along with a somewhat more expensive amine. Then,
A significant portion of heavy metal salts and other contaminants settle to the bottom as solid material. The excess light paraffin fraction and amine must then be removed. however,
Some amines may require care when using the motor oil later, while others may be left in the recycled product.

Johnson U.S. Patent No. 3879282
1.17Kg/cmG (170psig) and 132℃
(270〓) using phosphate-containing water in a closed autoclave. Significant amounts of contaminants and ash precipitate into the aqueous phase as insoluble metal phosphates. The preferred embodiment of the Johnson patent involves a specially constructed multi-stage facility using a preheater, a vigorously agitated pressure vessel, a phase separator, a settling tank and a strainer. Any remaining water in the gasoline and oil is removed in a flash distillation process. The recirculated water is then purified to a degree sufficient to recirculate it or to a degree severe enough to be disposed of into the environment. Filtration of the treated oil is carried out with silica gel to remove foreign matter, especially tetraethyl lead, which is not removed in the pretreatment.

The petroleum refining industry uses methods such as visbreaking, solvent deasphalting, hydrotreating, hydrocracking, coking, Houdresid fixed bed cracking, H-oil and fluid catalytic cracking to treat reduced crude. I've been researching.
One or more methods of processing blown crude oil to form transportation and heating fuels are described in U.S. Patent Application No. 904,216 (now U.S. Pat. No. 4,347,122), U.S. Pat. No. 094277 (currently U.S. Patent No. 4354923) and No. 094092
(now U.S. Pat. No. 4,332,673), these patents are incorporated by reference.

PROBLEM SOLVED BY THE INVENTION The method of the above-mentioned U.S. patent application involves contacting extracted crude oil with a hot regenerated catalyst in a riser cracking zone with a short contact time and discharging the catalyst and products through an exhaust riser. This method utilizes the moment difference between the catalyst particles and the catalyst particles for instant separation. The catalyst is stripped and sent to a regeneration zone, and the regenerated catalyst is recycled back to the riser to repeat the cycle. The high Conradson carbon value of the feedstock results in high coke deposits on the catalyst, amounting to as much as 12% by weight based on the feedstock. Because of these high coke levels, the temperature inside the regenerator can become excessive, sometimes exceeding 760°C (1400°C)816
℃ (1500〓), which can cause the active cracking component of the FCC catalyst (crystalline aluminum silicate zeolite) to undergo hydrogen decomposition and rapidly deactivate, and the equipment to be metallurgically damaged.

(Means for Solving the Problems) In the present invention, existing petroleum refining equipment can be used and only needs to be slightly modified for co-production of recycled motor oil. Particularly useful equipment for purposes of the present invention are purification equipment known as carbon and metal removal systems (MRS), such as those described in Bartholic U.S. Pat. No. 4,325,817 and U.S. Pat. be. Related technology is disclosed in U.S. Patent Application No. 355661 (March 3, 1982).
(Japanese filing).

In a preferred embodiment of the invention, the waste lubricating oil is
The oil is pumped into a small standpipe installed laterally along the MRS equipment, and the oil is gently evaporated at temperatures ranging from 316°C to 510°C (600° to 950°C) to separate lubricant contaminants and ash. Collect and recirculate to the lubricating oil treatment plant. The sorbent from the MRS treatment unit carrying ash and sludge is
It is either discarded or recycled in the same way as used (contaminated) sorbent from conventional purification units.

FIG. 1 is a schematic diagram of a preferred apparatus for practicing the invention.

The device of the present invention is composed of a combustor, a first contactor, a second contactor, cooling means and a receiver. The entrances and exits of each equipment element mentioned above are as follows.

The combustor has at least two inlets, hereinafter referred to as a regeneration gas inlet and a spent catalyst inlet, and at least two inlets, hereinafter referred to as a regeneration gas outlet and an active catalyst outlet.
It has multiple exits. The first contactor has an activated catalyst inlet of the first contactor, a quenching agent inlet of the first contactor, a first
at least four inlets, hereinafter referred to as a feedstock inlet of the contactor and a stripping steam inlet of the first contactor, and a spent catalyst outlet of the first contactor and a product outlet of the first contactor; It has at least two outlets called. The second contactor includes a second contactor active catalyst inlet, a second contactor quenchant inlet, a second
at least four inlets, hereinafter referred to as the feedstock inlet of the contactor and the stripping steam inlet of the second contactor, and at least four inlets, hereinafter referred to as the waste catalyst outlet of the second contactor and the product outlet of the second contactor; 2
It has multiple exits.

The above-mentioned devices with corresponding entrances and exits are combined as follows. The regeneration gas inlet is connected to a source of oxidizing gas. The spent catalyst inlet is connected to the first contactor spent catalyst outlet as well as the second contactor spent catalyst outlet so that the solid spent catalyst can be transferred to the combustor for regeneration. The active catalyst outlet is connected to the first contactor active catalyst inlet and the second contactor active catalyst inlet so that the solid active catalyst can move to the first and/or second contactor and contact the feedstock. It's getting old. The regeneration gas outlet is connected to means for enriching the oxidizing gas before being recycled again. The active catalyst inlet of the first contactor is connected to the combustor as described above. The quenchant inlet of the first contactor is connected to a source of atomized material such as water and steam. The feed inlet of the first contactor is connected to a source of heavy hydrocarbons, such as residual oil. 1st
The contactor stripping steam inlet is connected to a source of stripping gas, such as steam. The first contactor product outlet is connected to a receiver and preferably thereafter passed to recirculation means.

The active catalyst inlet of the second contactor is connected to the combustor as described above, and the second contactor quenchant inlet is connected to a source of atomized material, such as water and steam. The feedstock inlet of the second contactor contains contaminated specified hydrocarbons, such as used motor oil.
-lized hydrocarbon) feedstock source. The second contactor stripping steam inlet is connected to a source of stripping gas, such as steam. Second
The contactor product outlet is connected to a receiver and preferably thereafter passed to cooling means. Those skilled in the art will appreciate that the invention is not limited to the examples and descriptions given above, and that numerous modifications and changes are possible without departing from the invention. For example, it is not necessary to use all contactors at the same time. The active and waste catalyst tubes may communicate independently from and to the combustor or may be in the form of a manifold. A number of second contactors may be connected to the combustor in parallel configuration with the first contactor. Also, a number of contactors may be connected in series from the feedstock to the product direction, in which case the contactors are not operated independently from the feedstock to the final product process.
The products become partially purified second and third feedstocks.

Feedstock oil such as residual oil with an initial boiling point of 350℃ or higher,
Via conduit 3 it is introduced into a first contactor 22 where the feedstock is brought into contact with solid active sorbent granules that have little cracking activity under the conditions of use. These conditions of use include thermal vis-breaking,
Conditions that reduce metal contaminants to acceptably low levels and reduce the Conradson carbon value of the feedstock. The first contactor 22 has a riser reactor 5 (hereinafter referred to as the first riser) which reacts the feedstock oil containing metal contaminants with no or little catalytic cracking activity. This device substantially removes metals without excessively thermally decomposing the feedstock oil by thermally contacting it with active solid sorbent particles. Water mist is added to the feedstock in conduit 1. The feedstock is introduced by conduit 3 into the first riser 5 above the bottom. The steam in conduit 7 and/or the steam mixed with water in conduit 9 is mixed with the circulated hot solid granules at the bottom of the first riser. The amount and conditions are chosen so as to adjust the temperature of the regenerated thermal solids not yet in contact with the feedstock oil to a temperature specifically selected for feeding into the first riser 5. If desired, a "wet gas" (eg, light hydrocarbons) or other lifting gas may be used to convey the granules to the first riser 5. First riser pipe 5
The suspended material is discharged from the top or open end of the riser, and the hot visbreaking hydrocarbon vapors and diluent gas are transferred to a plurality of parallel tubes located around the upper open end of the riser contact area. When passing through the arranged cyclone separators 11 and 13, it is separated from fine particles. Cyclone separators 11 and 1
The hydrocarbon vapors separated from the solids by 3 are collected in a plenum chamber and then withdrawn and recovered in conduit 17. Solid particulates of waste sorbent that accumulate metal precipitates and contain carbonaceous material from pyrolysis are collected at the bottom of vessel 21.
The container 21 has a stripping section 23 to which stripping gas is supplied via a conduit 25. The stripped solid sorbent granules are passed to a granules fluidized bed at the bottom of the regeneration zone 29 by means of a standpipe 27 with a flow control valve 28 in the center. Similarly, the stripped solid granules from the second contactor are also transferred to the standpipe 11.
27 from the second contactor 1122 to the combustor 40
is passed through a fine bed at the bottom of the regeneration zone 29.

Regeneration or combustion support gas, such as oxygen modified gas or air, is supplied by conduit 31 through distribution plenum chamber 33 to the bottom of the regeneration zone. Distribution plenum chamber 33 supports a plurality of radial gas distribution pipes 35 . Regeneration of waste sorbent granules into active form involves combustion of carbonaceous deposits on and in the waste sorbent in an oxygen-containing gas;
This is achieved by converting CO, _CO2 and/or other combustion products. Combustion product gases and catalyst pass from the upper level 37 of the fluidized bed in the flue gases of fines to the upper enlargement of the regenerator where a combination of baffle settling means and a cyclone separator remove the solid particulates from the product flue. The gas is separated. The separated fine particles are passed through the narrow passageway 39 as a fluidized bed material 41.
are collected in an annular area around the The flue gas separated from the solids is arranged around the open upper end of the passageway 39. It passes through a plurality of cyclones 43 and the accompanying fine powder is removed. This flue gas then passes through plenum chamber 45 and is withdrawn by conduit 47. The regenerated and activated solid sorbent granules are passed through the standpipe 49 to the bottom of the first riser 5 and used for the application proposed here.

Similarly, active solid sorbent granules are fed to the second contactor 1122 at standpipe 1149. A portion of the hot active sorbent is withdrawn from conduit 51 and sent to heat exchanger 53 where it is transferred to conduit 55.
450 pounds of steam is generated through indirect heat exchange with boiler feed water introduced from the This water vapor is recovered via conduit 57. The partially cooled solid particles are extracted from the conduit 59 and transferred to the regeneration zone 29.
It is fed to the bottom of the fine fluidized bed at the bottom of the bed and used to control the temperature of the metal-contaminated fine particles to be regenerated.

This contaminant removal system includes a second contactor 112
2, which, like the first contactor 22, has a
Connected to combustor 40 by conduits 1127 and 1149. Contaminated specified hydrocarbon raw materials such as used motor oil with an initial boiling point of 100℃ or higher,
introduced into the second contactor 1122 via the conduit 113;
The contaminated specified hydrocarbon is then contacted with active solid sorbent granules that have little cracking activity under the conditions of use. The conditions of use are to reduce metals and other contaminants that boil above the initial boiling point of the contaminated specified hydrocarbon.
These are the conditions necessary to substantially remove contaminated identified hydrocarbon contaminants. Second contactor 1
122 has a riser 115; (Hereinafter, the second
(referred to as a riser). This involves selectively thermally contacting a specified hydrocarbon feedstock containing metal-containing contaminants and other high-boiling point contaminants with active solid sorbent granules that have little or no cracking activity. This device substantially removes contaminants without excessively thermally decomposing hydrogen. Water mist is added to the contaminated specified hydrogen feed through conduit 1111 and the feed is transferred via conduit 113 to second riser 1.
15 above the bottom. conduit 11
7 and/or the steam mixed with water in conduit 119 is mixed with circulating heat solid particles at 350°C to 500°C at the bottom of the second riser. The amounts and conditions are such that the temperature of the hot solids exiting the regeneration and not yet in contact with the contaminated specified hydrocarbon feedstock is adjusted to a temperature specifically selected for supply to the second riser. It is. If desired, "wet gas" (eg, light hydrocarbons) or other lifting gas may be used to convey the granules to the second riser 115. Mixing the diluent and solids in a specific combination results in a vertical velocity component appropriate to the solids prior to contact with the dispersed feedstock of contaminated specified hydrocarbons in the downcomer under specific temperature and pressure conditions. can be granted. A suspension of solid sorbent fines and a low partial pressure contaminated specified hydrocarbon feedstock atomization in a steam diluent has a
At temperatures below 0.degree. C., hydrocarbons are withdrawn from riser 115 at a rate that provides a residence time of less than 3 seconds, preferably in the range of 1 to 2.8 seconds. 2nd riser pipe 1
15 is fitted with a plurality of vertically spaced feed inlets, which vary the hydrocarbon residence times previously mentioned. The active sorbent/contaminated specified hydrocarbon feed ratio is preferably in the range of about 3 to 12. The suspended material passing through the riser 115 is discharged from the top of the riser, i.e. its open end;
A plurality of cyclone separators 1111 and 1 arranged in parallel around the upper open end of the riser contact area
113 through which hydrocarbon vapor and diluent gas are passed and separated from solids. Atomized hydrocarbons and/or hydrocarbon vapors separated from entrained solids by a cyclone separator are transferred to plenum chamber 1115.
and then withdrawn and recovered through conduit 1117 at a temperature below about 480°C. The accompanying hydrocarbons are transferred to conduit 1176 and cooling means 1 if desired.
170 and enters collection container 1172. Solid particulate waste sorbent with accumulated metal deposits and containing carbonaceous material is collected at the bottom of the container 1121;
The container 1121 has a stripping section 1123 to which stripping gas is supplied from a conduit 1125 at a temperature of about 200 DEG C. or higher. High slipping temperatures of up to 580°C are also possible. The stripped solid sorbent granules are passed to a granules fluidized bed at the bottom of the regeneration zone 1128 by a standpipe 1127 with a central flow control valve. This is similar to the case where the first riser pipe 5 passes through the stand pipe 27. The regenerated and activated sorbent enters the second riser 115 from the standpipe 1149 and is used for the proposed use. This is also the same as when entering the first riser pipe 5 from the stand pipe 49.

Those skilled in the art will understand that the invention is not limited to the examples and descriptions given above and that many modifications and changes are possible without departing from the invention. For example, several specified hydrocarbon pollutant removal combustors may be mounted in parallel to a single catalytic combustion contactor. Or again,
It is also possible to connect several contaminant removers in series to remove contaminants from the specified hydrocarbon in stages. If desired, the solid sorbent with negligible catalytic activity can be diluted with another type of granule, the diluent being essentially inert, even if it is such that it will interact with the specified hydrocarbon. It may be an active substance. Many other variations are possible, both in terms of equipment design and process operation.

(Effects of the Invention) Improvement of used motor oil by removing deteriorating components and other contaminants makes it possible to provide a recycled and reusable motor oil, which is a detergent-inhibitor. It is added to new motor oil or mixed into new motor oil as an inexpensive base material. Used motor oil, with or without partial removal of contaminants and ash, has previously been used only as a rust inhibitor in equipment and machinery, and as an additive ingredient in hydrocarbon fuels. .

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a preferred apparatus for practicing the invention.

Claims (1)

[Scope of Claims] 1 (a) The first contactor contains a fine particulate low catalytic capacity sorbent substantially free of used lubricating oil and heated at 343°C (650°C).
〓) contacting with a carbon-metallic feedstock containing material boiling above to produce a purified product and a sorbent contaminated by contact with said carbon-metallic feedstock; (b) separating said purified product from said contaminated sorbent formed on contact with said carbon-metallic feed; (c) said carbon-metallic feed; The carbon-metallic feedstock is prepared by heating the contaminated sorbent formed upon contact with the feedstock to between about 533°C and about 683°C in the presence of an oxygen-containing gas. regenerating said contaminated sorbent formed on contact with oil; (d) withdrawing a small portion of the regenerated particulate sorbent and passing it through a second smaller contactor; (e) heating said regenerated particulate sorbent portion in said second contactor with contaminated used lubricating oil at a temperature of about 350-500° C. for a period of time ranging from about 1 to 3 seconds;
(f) contacting the used lubricating oil of (e) above at a temperature of (g) separating the contaminated sorbent formed from the product formed in said second contactor; returning the contaminated sorbent to a regenerator for regeneration and recycling to said first contactor. 2. The method of claim 1, wherein said contaminated used lubricating oil comprises used lubricating oil. 3. Per kilogram of the above used lubricating oil,
2. The method of claim 1, wherein about 3 to 12 kilograms of said particulate sorbent are contacted.