CA1275958C - Treatment of petroleum derived organic sludges and oil residues - Google Patents
Treatment of petroleum derived organic sludges and oil residuesInfo
- Publication number
- CA1275958C CA1275958C CA000529379A CA529379A CA1275958C CA 1275958 C CA1275958 C CA 1275958C CA 000529379 A CA000529379 A CA 000529379A CA 529379 A CA529379 A CA 529379A CA 1275958 C CA1275958 C CA 1275958C
- Authority
- CA
- Canada
- Prior art keywords
- oil residues
- temperature
- sludges
- pyrolytic oils
- organic matter
- 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 - Lifetime
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Abstract of the Disclosure A method of producing pyrolytic oils suitable for petroleum reprocessing is disclosed. According to the invention, petroleum derived organic sludges or oil residues in a solid/liquid phase are subjected to vacuum pyrolysis under temperature and sub-atmospheric pressure conditions such as to prevent gas and vapor phase secondary cracking reactions and to thereby increase the yield of pyrolytic oils to the detriment of hydrocarbon gases. About 97% of the organic matter content of the sludges and about 75% of the organic matter content of the oil residues can be con-verted into pyrolytic oils suitable for petroleum reproces-sing.
Description
~L2s7~i9~
The present inYention relates to a method of treating petroleum derived organic sludges and oil residues.
The treatment of organic sludges derived from the biodegradation units of petroleum indus-tries presents a major problem for such a type of industry. Such organic sludges are also termed activated sludges when the biodegradation is con-ducted under aerobic conditions; on the other hand, when the biodegradation is carried out under anaero-bic conditions, the sludges are referred to as biological sludyes. Due to their solid/liquid nature, these sludyes cannot be treated by conven-tional distillation techniques to obtain useful products and therefore they must be disposed of at considerable cost generally by incineration.
Oil residues which have a higher content of inorganic matter (e.g. sand) but a lesser content of water than organic sludges of petroleum origin also presents a similar disposal problem. Such oil residues can be for example spilled hydrocarbon oils which are removed together with sand used to limit the oil spill.
Applicant has already proposed in Canadian patent application No. 509,162, filed May 1~, 1986, a process for the treatment of used rubber tires by vacuum pyroIysis to produce liquid and gaseous hydrocarbons and a solid carbonaceous material, the liquid hydrocarbons produced beiny suitable for use as heating fuel. Accordiny to this process, the pyrolysis of the tires is carried out at a tempera-ture in the range of about 360C to about 415C, under a sub-atmospheric pressure of less than about 35 mm ~g and such that the gases and vapors produced in the reactox have a residence time of the order of a few seconds. In this manner, the formation of liquid hydrocarbons is promoted so that high yields of hydrocarbon oils are obtained.
It has now been found quite unexpectedly that petroleum derived organic sludges and oil residues can also be treated by vacuum pyrolysis, to produce pyrolytic oils which are suitable for reprocessing in petroleum refineries.
Accordingly, the present invention provides a method of producing pyrolytic oils suitable for petroleum reprocessing, which comprises subjecting petroleum-derived organic sludges or oil residues in a solid/liquid phase to vacuum pyrolysis under temperature and sub-atmospheric pres-sure conditions such as to prevent gas and vapor phase second-ary cracking reactions and thereby to increase the yield of pyrolitic oils to the detriment of hydrocarbon gases.
The desired pyrolytic oils are advantageously obtained by carrying the pyrolysis of the organic sludges or oil residues at a temperature in the range of about 380C
to about 450C, preEerably at about 410C, and under a sub-atmospheric pressure of less than about 50 mm Hg (absolute pressure). Operatlng at a temperature of about 410C has been found to promote the formation of the pyrolytic oils, thereby significantly increasing the yield thereo~.
According to a preferred embodiment of the inven-tion, the organic sludges or oil residues are fe~ to a reac-tor, the pressure within the latter is : ., -~L~7~
reduced to about 5 mm ~Ig (absolute pressure) and the feed material is then ~radually heated up to about 410C. The material is maintained at such a tempera-ture and under a sub-atmospheric pressure not exceeding about 50 mm Hg (absolute pressure) until substantially complete conversion oE the organic matter content of the sludges or oil residues into pyrolytic oils. The condensable pyrolytic vapors generated as a result of the pyrolysis are withdrawn from the reactor and passed through suitable heat exchanger units to condense and thereby provide the desired pyrolytic oils.
The method according to the invention is non-destructive and thus enables one to convert ; about 97~ of the organic matter content of the sludges and about 75~ of the organic matter content of the oil residues, into pyrolytic oils suitable for petroleum reprocessing. The sterile residual solid which is obtained as a secondary product in the method of the invention and which is composed ' mostly of inorganic matter such as sand can be safely disposed of by burial underground, without contaminating the environment.
Further features and advantages of the ; invention will become more readily apparent from the following description of preferred embodiments, with reference to the appended drawings, in which:
Fig. l is a plot of the product yield as a function of tempera-ture, in a method according to the invention;
~Z~75~3~8 Figs. 2A and 2B are chromatograms respect-ively of the pyrolytic oils obtained at 497C from an oil residue sample and of the oils extracted with dichloromethane from the same sample;
Figs. 3A and 3B are chromatograms respect-ively of the pyrolytic oils obtained at 108C from an oil residue sample and of commercial diesel fuel;
and Figs. 4A and 4s are chromatograms respect-ively of the pyrolytic oils obtained from an oil residue sample and of the pyrolytic oils obtained from an activated sludge sample.
An oil residue sample containing about 34weight % organic matter, about 51 weight % inorganic matter and about 15 weight % water was subjected to vacuum pyrolysis and the pyrolytic products were analysed for their composition as a function of temperature. The following results were obtained, as calculated on moisture and ash free basis:
Temperature Yields (weight)%
t C) Pyrolytic Total ~esidual Gases OllsWaterSolids 108 18.80.0 80.2 1.0 198 41.70.0 57.7 0.6 316 45.61.9 51.8 0.7 407 49.35,7 43.0 2.0 497 50.86.0 40.4 2.8 ~2~7~958 The above data is reported in Fig. 1. As shown, substantially maximum production of pyrolytic oils is obtained in the temperature range of about 380 - 450C, the op-timu~ temperature being about 410C.
The chemical analysis of the pyrolytic oils produced at the above temperatures is as follows:
Elementary Analysis Humi- Calorific T dity Value ( C) C H N S O (%) (kcal kg 108 85.8 13.2 0.70.3 0.0 0~0 11,190 198 85.9 13.1 0.40.6 0.0 0.1 11,060 316 85.5 13.0 0.90.6 0.0 0.3 11,020 407 86.3 12.9 0.20.6 0.0 0.1 10,800 497 85.7 12.8 0.90.6 0.0 0.1 10,850 The above data show that the pyrolytic oils are similar to unrefined petroleum, the oils being rich in carbon and hydrogen with a total content in nitrogen, sulfur and oxygen of less than 2%. The pyrolytic oils have a moisture content which ls negligable and a high calorific value which decreases slightly as the temperature of the pyroly-sis increases.
For the purpose of comparison, the same oil residue sample was e~tracted with dichloro-methane using a soxhlet. The oils extracted from ;95~
the sample were analysed by gas chromatography and the chromatogram thereof was compared with that of the oils obtained by vacuum pyrolysis at 497C. As shown in Figs. 2A and 2s, the pyrolytic oils are similar in structure to the oils obtained by non-destructive methods, such as by soxhlet extraction.
This comparative test clearly shows that the method according to the invention is also non-destructive.
The pyrolytic oils produced at 108C were also compared by gas chromatography with commercial diese] fuel. As shown in Figs. 3A and 3B, both are composed of elements having similar boiling points.
The pyrolytic oils obtained from the oil residue sample were further tested for their suitability to being reprocessed in petroleum refineries. The following results were obtained:
API Gravity (ASTM D1298) 29.0 Specific Gravity 0.8816 Flash Point (ASTM D93) 178F
Sulphur 0.90 %
B.S. & W. (ASTM D4007) 0.20 %
Viscosity @ 100 F, Kinematic 0.0716 Stokes Ramsbottom Carbon Residue (ASTM D524) 0.13 Distillation (ASTM D86) ~ IBP 486 F
:
5% 505 10~ 520 20~ 539 30~ 555 40~ 574 .
~27~9i5~3 50% 594 60% 617 70% 644 80% 686 90% 746 93% 760 (~esidue Breakdown) The metals identified in the pyrolytic oils produced at 407C were the following: -~
, . ~.
Metals Concentration (ppm) Vanadium 3 Nickel 0.3 Sodium 330 Copper 0O8 Iron 6.8 ::
The above data clearly show that the oils produced by vacuum pyrolysis frcm oil residues are suitable for petroleum reprocessing. The concentra-tions of V, Ni, Cu and Fe metals which could act as catalyst poisons are within the acceptable limits.
The concentration o~ Na which must be lower than 1 ppm to avoid catalyst poisoning can be reduced by a desalting process such as that normally encountered in petroleum refining.
An organic sludge sample containing about 34 weight % organic matter, about 3 weight % inorga-nic matter and about 63 weight % water was similarly trea-ted by vacuum pyrolysis. The pyrolytic oils 7S~58 produced from the sample were analysed by gas chromatography and the chromatogram thereof was compared with that of the pyrolytic oils produced from the aforesaid oil residue sample~ As shown in Figs. 4A and 4B, the pyrolytic oils produced from both samples are essentially the same. The peaks representative of Cg -C20 hydrocarbons are easily identified.
:' ~
: : : ' .:
~: :
.
.
.
The present inYention relates to a method of treating petroleum derived organic sludges and oil residues.
The treatment of organic sludges derived from the biodegradation units of petroleum indus-tries presents a major problem for such a type of industry. Such organic sludges are also termed activated sludges when the biodegradation is con-ducted under aerobic conditions; on the other hand, when the biodegradation is carried out under anaero-bic conditions, the sludges are referred to as biological sludyes. Due to their solid/liquid nature, these sludyes cannot be treated by conven-tional distillation techniques to obtain useful products and therefore they must be disposed of at considerable cost generally by incineration.
Oil residues which have a higher content of inorganic matter (e.g. sand) but a lesser content of water than organic sludges of petroleum origin also presents a similar disposal problem. Such oil residues can be for example spilled hydrocarbon oils which are removed together with sand used to limit the oil spill.
Applicant has already proposed in Canadian patent application No. 509,162, filed May 1~, 1986, a process for the treatment of used rubber tires by vacuum pyroIysis to produce liquid and gaseous hydrocarbons and a solid carbonaceous material, the liquid hydrocarbons produced beiny suitable for use as heating fuel. Accordiny to this process, the pyrolysis of the tires is carried out at a tempera-ture in the range of about 360C to about 415C, under a sub-atmospheric pressure of less than about 35 mm ~g and such that the gases and vapors produced in the reactox have a residence time of the order of a few seconds. In this manner, the formation of liquid hydrocarbons is promoted so that high yields of hydrocarbon oils are obtained.
It has now been found quite unexpectedly that petroleum derived organic sludges and oil residues can also be treated by vacuum pyrolysis, to produce pyrolytic oils which are suitable for reprocessing in petroleum refineries.
Accordingly, the present invention provides a method of producing pyrolytic oils suitable for petroleum reprocessing, which comprises subjecting petroleum-derived organic sludges or oil residues in a solid/liquid phase to vacuum pyrolysis under temperature and sub-atmospheric pres-sure conditions such as to prevent gas and vapor phase second-ary cracking reactions and thereby to increase the yield of pyrolitic oils to the detriment of hydrocarbon gases.
The desired pyrolytic oils are advantageously obtained by carrying the pyrolysis of the organic sludges or oil residues at a temperature in the range of about 380C
to about 450C, preEerably at about 410C, and under a sub-atmospheric pressure of less than about 50 mm Hg (absolute pressure). Operatlng at a temperature of about 410C has been found to promote the formation of the pyrolytic oils, thereby significantly increasing the yield thereo~.
According to a preferred embodiment of the inven-tion, the organic sludges or oil residues are fe~ to a reac-tor, the pressure within the latter is : ., -~L~7~
reduced to about 5 mm ~Ig (absolute pressure) and the feed material is then ~radually heated up to about 410C. The material is maintained at such a tempera-ture and under a sub-atmospheric pressure not exceeding about 50 mm Hg (absolute pressure) until substantially complete conversion oE the organic matter content of the sludges or oil residues into pyrolytic oils. The condensable pyrolytic vapors generated as a result of the pyrolysis are withdrawn from the reactor and passed through suitable heat exchanger units to condense and thereby provide the desired pyrolytic oils.
The method according to the invention is non-destructive and thus enables one to convert ; about 97~ of the organic matter content of the sludges and about 75~ of the organic matter content of the oil residues, into pyrolytic oils suitable for petroleum reprocessing. The sterile residual solid which is obtained as a secondary product in the method of the invention and which is composed ' mostly of inorganic matter such as sand can be safely disposed of by burial underground, without contaminating the environment.
Further features and advantages of the ; invention will become more readily apparent from the following description of preferred embodiments, with reference to the appended drawings, in which:
Fig. l is a plot of the product yield as a function of tempera-ture, in a method according to the invention;
~Z~75~3~8 Figs. 2A and 2B are chromatograms respect-ively of the pyrolytic oils obtained at 497C from an oil residue sample and of the oils extracted with dichloromethane from the same sample;
Figs. 3A and 3B are chromatograms respect-ively of the pyrolytic oils obtained at 108C from an oil residue sample and of commercial diesel fuel;
and Figs. 4A and 4s are chromatograms respect-ively of the pyrolytic oils obtained from an oil residue sample and of the pyrolytic oils obtained from an activated sludge sample.
An oil residue sample containing about 34weight % organic matter, about 51 weight % inorganic matter and about 15 weight % water was subjected to vacuum pyrolysis and the pyrolytic products were analysed for their composition as a function of temperature. The following results were obtained, as calculated on moisture and ash free basis:
Temperature Yields (weight)%
t C) Pyrolytic Total ~esidual Gases OllsWaterSolids 108 18.80.0 80.2 1.0 198 41.70.0 57.7 0.6 316 45.61.9 51.8 0.7 407 49.35,7 43.0 2.0 497 50.86.0 40.4 2.8 ~2~7~958 The above data is reported in Fig. 1. As shown, substantially maximum production of pyrolytic oils is obtained in the temperature range of about 380 - 450C, the op-timu~ temperature being about 410C.
The chemical analysis of the pyrolytic oils produced at the above temperatures is as follows:
Elementary Analysis Humi- Calorific T dity Value ( C) C H N S O (%) (kcal kg 108 85.8 13.2 0.70.3 0.0 0~0 11,190 198 85.9 13.1 0.40.6 0.0 0.1 11,060 316 85.5 13.0 0.90.6 0.0 0.3 11,020 407 86.3 12.9 0.20.6 0.0 0.1 10,800 497 85.7 12.8 0.90.6 0.0 0.1 10,850 The above data show that the pyrolytic oils are similar to unrefined petroleum, the oils being rich in carbon and hydrogen with a total content in nitrogen, sulfur and oxygen of less than 2%. The pyrolytic oils have a moisture content which ls negligable and a high calorific value which decreases slightly as the temperature of the pyroly-sis increases.
For the purpose of comparison, the same oil residue sample was e~tracted with dichloro-methane using a soxhlet. The oils extracted from ;95~
the sample were analysed by gas chromatography and the chromatogram thereof was compared with that of the oils obtained by vacuum pyrolysis at 497C. As shown in Figs. 2A and 2s, the pyrolytic oils are similar in structure to the oils obtained by non-destructive methods, such as by soxhlet extraction.
This comparative test clearly shows that the method according to the invention is also non-destructive.
The pyrolytic oils produced at 108C were also compared by gas chromatography with commercial diese] fuel. As shown in Figs. 3A and 3B, both are composed of elements having similar boiling points.
The pyrolytic oils obtained from the oil residue sample were further tested for their suitability to being reprocessed in petroleum refineries. The following results were obtained:
API Gravity (ASTM D1298) 29.0 Specific Gravity 0.8816 Flash Point (ASTM D93) 178F
Sulphur 0.90 %
B.S. & W. (ASTM D4007) 0.20 %
Viscosity @ 100 F, Kinematic 0.0716 Stokes Ramsbottom Carbon Residue (ASTM D524) 0.13 Distillation (ASTM D86) ~ IBP 486 F
:
5% 505 10~ 520 20~ 539 30~ 555 40~ 574 .
~27~9i5~3 50% 594 60% 617 70% 644 80% 686 90% 746 93% 760 (~esidue Breakdown) The metals identified in the pyrolytic oils produced at 407C were the following: -~
, . ~.
Metals Concentration (ppm) Vanadium 3 Nickel 0.3 Sodium 330 Copper 0O8 Iron 6.8 ::
The above data clearly show that the oils produced by vacuum pyrolysis frcm oil residues are suitable for petroleum reprocessing. The concentra-tions of V, Ni, Cu and Fe metals which could act as catalyst poisons are within the acceptable limits.
The concentration o~ Na which must be lower than 1 ppm to avoid catalyst poisoning can be reduced by a desalting process such as that normally encountered in petroleum refining.
An organic sludge sample containing about 34 weight % organic matter, about 3 weight % inorga-nic matter and about 63 weight % water was similarly trea-ted by vacuum pyrolysis. The pyrolytic oils 7S~58 produced from the sample were analysed by gas chromatography and the chromatogram thereof was compared with that of the pyrolytic oils produced from the aforesaid oil residue sample~ As shown in Figs. 4A and 4B, the pyrolytic oils produced from both samples are essentially the same. The peaks representative of Cg -C20 hydrocarbons are easily identified.
:' ~
: : : ' .:
~: :
.
.
.
Claims (7)
1. A method of producing pyrolytic oils suitable for petroleum reprocessing, which comprises subjecting petro-leum-derived organic sludges or oil residues in a solid/liquid phase to vacuum pyrolysis under temperature and sub-atmospheric pressure conditions such as to prevent gas and vapor phase secondary cracking reactions and thereby to increase the yield of pyrolytic oils to the detriment of hydrocarbon gases.
2. A method as claimed in claim l, wherein the pyrolysis is carried out at a temperature in the range of about 380°C to about 450°C and under a sub-atmospheric pressure of less than about 50 mm Hg (absolute pressure).
3. A method as claimed in claim 2, wherein said temperature is about 410°C.
4. A method as claimed in claim l, wherein the organic sludges or oil residues are gradually heated up to a temperature in the range of about 380°C to about 450°C, under a sub-atmospheric pressure of about 5 mm Hg (absolute pressure), and maintained at said temperature while under a sub-atmospheric pressure not exceeding about 50 mm Hg (absolute pressure) until substantially complete conversion of the content in organic matter of said organic sludges or oil residues into said pyrolytic oils.
5. A method as claimed in claim 4, wherein said temperature is about 410°C.
6. A method as claimed in claim 2, wherein said organic sludges contain organic matter and about 97% of said organic matter is converted into said pyrolytic oils.
7. A method as claimed in claim 2, wherein said oil residues contain organic matter and about 75% of said organic matter is converted into said pyrolytic oils.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000529379A CA1275958C (en) | 1987-02-10 | 1987-02-10 | Treatment of petroleum derived organic sludges and oil residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000529379A CA1275958C (en) | 1987-02-10 | 1987-02-10 | Treatment of petroleum derived organic sludges and oil residues |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1275958C true CA1275958C (en) | 1990-11-06 |
Family
ID=4134940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529379A Expired - Lifetime CA1275958C (en) | 1987-02-10 | 1987-02-10 | Treatment of petroleum derived organic sludges and oil residues |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1275958C (en) |
-
1987
- 1987-02-10 CA CA000529379A patent/CA1275958C/en not_active Expired - Lifetime
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0140811B1 (en) | Processes and apparatus for the conversion of sludges | |
| Vitolo et al. | Treatment of olive oil industry wastes | |
| Zabaniotou et al. | Pyrolysis of used automobile tires and residual char utilization | |
| Conesa et al. | Study of the thermal decomposition of petrochemical sludge in a pilot plant reactor | |
| EP0588814B1 (en) | Treatment of automobile shredder residue by vacuum pyrolysis | |
| Díez et al. | Pyrolysis of tyres: A comparison of the results from a fixed-bed laboratory reactor and a pilot plant (rotatory reactor) | |
| Konar et al. | Fuels and chemicals from sewage sludge: 3. Hydrocarbon liquids from the catalytic pyrolysis of sewage sludge lipids over activated alumina | |
| US4446012A (en) | Process for production of light hydrocarbons by treatment of heavy hydrocarbons with water | |
| US5064523A (en) | Process for the hydrogenative conversion of heavy oils and residual oils, used oils and waste oils, mixed with sewage sludge | |
| BG62572B1 (en) | METHOD FOR PROCESSING OF VARIABLE OR WASTE PLASTICS | |
| JPS62256888A (en) | Hydroconversion method | |
| Chiang et al. | Element and PAH constituents in the residues and liquid oil from biosludge pyrolysis in an electrical thermal furnace | |
| US4449586A (en) | Process for the recovery of hydrocarbons from oil shale | |
| KR100265273B1 (en) | Emulsification Method and Apparatus of Waste Plastic | |
| SU1766265A3 (en) | Method of processing fluid products of low-temperature carbonization of hydrocarbon-containing raw material | |
| US4533460A (en) | Oil shale extraction process | |
| US4839021A (en) | Treatment of petroleum derived organic sludges and oil residues | |
| US4725350A (en) | Process for extracting oil and hydrocarbons from crushed solids using hydrogen rich syn gas | |
| US4428821A (en) | Oil shale extraction process | |
| EP1175376B1 (en) | Process and apparatus for the conversion of carbonaceous materials | |
| CA1275958C (en) | Treatment of petroleum derived organic sludges and oil residues | |
| US3707461A (en) | Hydrocracking process using a coal-derived ash | |
| US4551223A (en) | Thermal flashing of carbonaceous materials | |
| US4431511A (en) | Enhanced removal of nitrogen and sulfur from oil-shale | |
| Narangerel et al. | Hydrotreatment of Middle Distillate from Pyrolysis Tar by Using Fixed Bed Reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |