CA1100532A - Production of hydrocarbon liquids from solid carbonaceous materials - Google Patents
Production of hydrocarbon liquids from solid carbonaceous materialsInfo
- Publication number
- CA1100532A CA1100532A CA358,743A CA358743A CA1100532A CA 1100532 A CA1100532 A CA 1100532A CA 358743 A CA358743 A CA 358743A CA 1100532 A CA1100532 A CA 1100532A
- Authority
- CA
- Canada
- Prior art keywords
- materials
- tetralin
- hydrocarbon liquids
- carbonaceous material
- cellulosic
- 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
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/044—Smoking; Smoking devices
- A23B4/048—Smoking; Smoking devices with addition of chemicals other than natural smoke
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
C.R. Phillips and D.L. Granatstein ABSTRACT OF THE DISCLOSURE
Solid carbonaceous materials selected from the group consisting of glucose, lignite and cellulosic materials including wood, cellulose, paper, plant matter and the cellulosic fraction of municipal solid wastes are converted to hydrocarbon liquids by heating, under an atmosphere of air, in the presence of tetralin (tetrahydronaphthalene) and in the absence of a reducing gas, under autogenous pressure in a closed reactor vessel.
Solid carbonaceous materials selected from the group consisting of glucose, lignite and cellulosic materials including wood, cellulose, paper, plant matter and the cellulosic fraction of municipal solid wastes are converted to hydrocarbon liquids by heating, under an atmosphere of air, in the presence of tetralin (tetrahydronaphthalene) and in the absence of a reducing gas, under autogenous pressure in a closed reactor vessel.
Description
C.R. Phillips and D.L. Granatstein ~l~US3Z
PRODUCTION OF HYDROCARBON LIQUIDS FROM SOLID CARBONACEOUS MATERIALS
This invention relates to the conversion of solid carbonaceous materials such as glucose, lignite and cellulosic materials including wood, cellulose, paper, plant matter and the cellulosic fraction of muni-cipal solid wastes to a liquid hydrocarbon oil of high heating value.
Due to the widening gap between the supply of crude oil and the demand for liquid fuels, much research has been carried out on the con-version of renewable energy resources, such as wood, to liquid fuels.
Prior art processes suffer from many faults, among which are: the pro-ducts have less total heat content than the raw materials, the process requires costly reducing gases, often hydrogen, or the product is not readily utilized in conventional motors and power plants.
We have now discovered that such renewable energy resources as wood and plant matter, along with other solid carbonaceous materials such as glucose, lignite and cellulosic materials including paper and the cellulosic fraction of municipal solid wastes can be converted to a liquid hydrocarbon oil of high heating value by heating them under an atmosphere of air, in the presence of tetralin (tetrahydronaphthalene) and in the absence of a reducing gas, under autogenous pressure in a closed reactor vessel. The liquid product of this process can be utilized ` directly as a fuel oil or can be refined in the prior art manner to pro-duce gasoline or other hydrocarbons. In carrying out the process of our invention a net energy gain is achieved.
It is therefore an object of the present invention to convert solid carbonaceous materials to useful liquid hydrocarbons.
Other objects and advantages will be obvious from the following more detailed description of the invention:
In the practice of the invention, a high temperature, high pressure, stainless steel autoclave is employed to heat the solid car-bonaceous materials. Operating temperatures range from about 325C to about 400C, and the autogenous pressure produced during the reaction ranges from about 11.6-22 MPa (about 1700 to about 3200 psig~.
For convenience in slurrying and charging to the reactor, the solid carbonaceous material is usually ground to minus 65 mesh. How-ever successful runs have been carried out using particles up to 1/8 x 1/8 x 1/2 inches, and, due to the nature of the reaction, larger particles for example, wood chips, should work equally well.
A catalyst may be added to enhance the reaction rate. Catalysts which have been found to be effective in this reaction include nickel on kieselguhr (Girdler G-53 ~ , zirconium-promoted cobalt (Girdler G-67RS
TM), alumina- and calcium oxide-promoted iron oxide, molybdena, and nickel carbonate. Catalyst in an amount of 5 percent by weight of car-bonaceous material has been found to be suitable~
The carbonaceous material, with or without a catalyst, is slurried with tetralin in a ratio by weight of about 2:1 to about 3:1 tetralin to carbonaceous material, and this slurry is charged to the reactor in an atmosphere of air.
The carbonaceous materials, chosen from the group consisting of lignite, glucose and cellulosic materials including wood, cellulose, paper, plant matter and the cellulosic fraction of municipal solid wastes can be used bone dry, with excellent results. However, water may be present in the feed materials, and it has been found that water in a ratio of up to about 1:5 with respect to the carbonaceous material has ;; no ill effect on the practice of this invention.
After the feed material has been charged to the reactor and the reactor has been sealed, it is brought up to the operating temperature in the range of about 325C to about 400C, preferably about 350C, and is held at the operating temperature for about 15 to about 60 minutes, preferably about 30 minutes.
The reactor is then cooled to ambient temperature and the pro-ducts are separated into gases, benzene-soluble products, water-soluble products, and char. Benzene is removed by distilling to about 90C.
Unreacted tetralin and its dehydrogenated analogues, notably naphthalene, may be separated by distillation and rehydrogenated to tetralin for recycling, in the prior art manner, using the hydrogen 11~16~53z which has been produced as one of the product gases. The product oil can then be utilized as a high grade fuel oil, or can be upgraded to gasoline or other hydrocarbons in the prior art manner.
In tests to date, as much as 60 percent (dry basis) or more of the solid carbonaceous material has been converted to liquid hydrocarbons, equivalent to more than 3.5 barrels of oil per ton of dry carbonaceous material. Analysis reveals only trace amounts of N, S, and 0 present in the oil.
The heat content of the product oil is of the order of 44 MJ/kg (about 19000 Btu/lb).
It is believed that tetralin acts as a hydrogen-donor solvent which solubilizes the solid carbonaceous material while making available hydrogen in a readily acceptable form, more readily acceptable than gaseous hydrogen. In the ensuing hydrocracking, oxygen is stripped from ;.-the molecules, and a high heat content oil results.
The following examples illustrate the process of the present invention:
_ample 1 A slurry of 9.9 grams minus 65 mesh poplar (8.76 percent water) in 26.3 grams tetralin was reacted at 350C for 30 minutes in a 130 mL
rocking stainless steel autoclave. Pressure (autogenous) reached 2090 psig. Products consisted of 55.6 percent oil (C/H = 7.47, 19,600 Btu/lb) 27.4 percent gases (425 Btu/SCF, 47 mole percent H2), 11.7 percent char ;~ (14,000 Btu/lb) and 5.3 percent water. Total heat of combustion of these products (does not include tetralin or its reaction products) = 292.7 Btu. Heat of combustion of poplar feed = 178.3 Btu.
In the most severe case, all tetralin employed will be converted to naphthalene. After subtracting from the above example the hydrogen energy necessary to convert back to tetralin for recycle, the total heat of combustion of the products (not including tetralin) = 195.6 Btu, still greater than that of the feed poplar.
110c~53Z
Example 2 In the same autoclave as in Example 1, 14.2 grams glucose (dry), 0.63 grams Girdler G67RS catalyst, and 28.7 grams tetralin were slurried and reacted at 380C for 60 minutes. The product consisted of 57.3 per-cent oil, 25.8 percent gases, 14.1 percent water and 2.8 percent char.
Pressure reached 3200 psig.
Example 3 .
The test run of Example 2 was repeated using lOW30 motor oil in place of tetralin. Forty-five percent char and only 23.3 percent pro-duct oil resulted, and pressure reached 4150 psig after only 18 minutes.
PRODUCTION OF HYDROCARBON LIQUIDS FROM SOLID CARBONACEOUS MATERIALS
This invention relates to the conversion of solid carbonaceous materials such as glucose, lignite and cellulosic materials including wood, cellulose, paper, plant matter and the cellulosic fraction of muni-cipal solid wastes to a liquid hydrocarbon oil of high heating value.
Due to the widening gap between the supply of crude oil and the demand for liquid fuels, much research has been carried out on the con-version of renewable energy resources, such as wood, to liquid fuels.
Prior art processes suffer from many faults, among which are: the pro-ducts have less total heat content than the raw materials, the process requires costly reducing gases, often hydrogen, or the product is not readily utilized in conventional motors and power plants.
We have now discovered that such renewable energy resources as wood and plant matter, along with other solid carbonaceous materials such as glucose, lignite and cellulosic materials including paper and the cellulosic fraction of municipal solid wastes can be converted to a liquid hydrocarbon oil of high heating value by heating them under an atmosphere of air, in the presence of tetralin (tetrahydronaphthalene) and in the absence of a reducing gas, under autogenous pressure in a closed reactor vessel. The liquid product of this process can be utilized ` directly as a fuel oil or can be refined in the prior art manner to pro-duce gasoline or other hydrocarbons. In carrying out the process of our invention a net energy gain is achieved.
It is therefore an object of the present invention to convert solid carbonaceous materials to useful liquid hydrocarbons.
Other objects and advantages will be obvious from the following more detailed description of the invention:
In the practice of the invention, a high temperature, high pressure, stainless steel autoclave is employed to heat the solid car-bonaceous materials. Operating temperatures range from about 325C to about 400C, and the autogenous pressure produced during the reaction ranges from about 11.6-22 MPa (about 1700 to about 3200 psig~.
For convenience in slurrying and charging to the reactor, the solid carbonaceous material is usually ground to minus 65 mesh. How-ever successful runs have been carried out using particles up to 1/8 x 1/8 x 1/2 inches, and, due to the nature of the reaction, larger particles for example, wood chips, should work equally well.
A catalyst may be added to enhance the reaction rate. Catalysts which have been found to be effective in this reaction include nickel on kieselguhr (Girdler G-53 ~ , zirconium-promoted cobalt (Girdler G-67RS
TM), alumina- and calcium oxide-promoted iron oxide, molybdena, and nickel carbonate. Catalyst in an amount of 5 percent by weight of car-bonaceous material has been found to be suitable~
The carbonaceous material, with or without a catalyst, is slurried with tetralin in a ratio by weight of about 2:1 to about 3:1 tetralin to carbonaceous material, and this slurry is charged to the reactor in an atmosphere of air.
The carbonaceous materials, chosen from the group consisting of lignite, glucose and cellulosic materials including wood, cellulose, paper, plant matter and the cellulosic fraction of municipal solid wastes can be used bone dry, with excellent results. However, water may be present in the feed materials, and it has been found that water in a ratio of up to about 1:5 with respect to the carbonaceous material has ;; no ill effect on the practice of this invention.
After the feed material has been charged to the reactor and the reactor has been sealed, it is brought up to the operating temperature in the range of about 325C to about 400C, preferably about 350C, and is held at the operating temperature for about 15 to about 60 minutes, preferably about 30 minutes.
The reactor is then cooled to ambient temperature and the pro-ducts are separated into gases, benzene-soluble products, water-soluble products, and char. Benzene is removed by distilling to about 90C.
Unreacted tetralin and its dehydrogenated analogues, notably naphthalene, may be separated by distillation and rehydrogenated to tetralin for recycling, in the prior art manner, using the hydrogen 11~16~53z which has been produced as one of the product gases. The product oil can then be utilized as a high grade fuel oil, or can be upgraded to gasoline or other hydrocarbons in the prior art manner.
In tests to date, as much as 60 percent (dry basis) or more of the solid carbonaceous material has been converted to liquid hydrocarbons, equivalent to more than 3.5 barrels of oil per ton of dry carbonaceous material. Analysis reveals only trace amounts of N, S, and 0 present in the oil.
The heat content of the product oil is of the order of 44 MJ/kg (about 19000 Btu/lb).
It is believed that tetralin acts as a hydrogen-donor solvent which solubilizes the solid carbonaceous material while making available hydrogen in a readily acceptable form, more readily acceptable than gaseous hydrogen. In the ensuing hydrocracking, oxygen is stripped from ;.-the molecules, and a high heat content oil results.
The following examples illustrate the process of the present invention:
_ample 1 A slurry of 9.9 grams minus 65 mesh poplar (8.76 percent water) in 26.3 grams tetralin was reacted at 350C for 30 minutes in a 130 mL
rocking stainless steel autoclave. Pressure (autogenous) reached 2090 psig. Products consisted of 55.6 percent oil (C/H = 7.47, 19,600 Btu/lb) 27.4 percent gases (425 Btu/SCF, 47 mole percent H2), 11.7 percent char ;~ (14,000 Btu/lb) and 5.3 percent water. Total heat of combustion of these products (does not include tetralin or its reaction products) = 292.7 Btu. Heat of combustion of poplar feed = 178.3 Btu.
In the most severe case, all tetralin employed will be converted to naphthalene. After subtracting from the above example the hydrogen energy necessary to convert back to tetralin for recycle, the total heat of combustion of the products (not including tetralin) = 195.6 Btu, still greater than that of the feed poplar.
110c~53Z
Example 2 In the same autoclave as in Example 1, 14.2 grams glucose (dry), 0.63 grams Girdler G67RS catalyst, and 28.7 grams tetralin were slurried and reacted at 380C for 60 minutes. The product consisted of 57.3 per-cent oil, 25.8 percent gases, 14.1 percent water and 2.8 percent char.
Pressure reached 3200 psig.
Example 3 .
The test run of Example 2 was repeated using lOW30 motor oil in place of tetralin. Forty-five percent char and only 23.3 percent pro-duct oil resulted, and pressure reached 4150 psig after only 18 minutes.
Claims (5)
1. A process for producing hydrocarbon liquids from solid carbona-ceous materials selected from the group consisting of glucose, lignite, and cellulosic materials including, wood, cellulose, plant matter, paper and the cellulosic fraction of municipal solid wastes comprising heating said materials in a closed reactor vessel in an atmosphere of air to a temperature in the range of about 325-400°C, in the presence of tetralin, wherein said tetralin is present in a ratio of about 2:1 to about 3:1 with respect to said carbonaceous material, for a period of about 15 to about 60 minutes to a final pressure of about 11.6-22 MPa (about 1700 to about 3200 psig), thereby to produce said hydrocarbon liquids.
2. The process of claim 1 wherein said materials are heated for a period of 30 minutes.
3. The process of claim 1 wherein said materials are heated to a temperature of 350°C.
4. The process of claim 1 wherein a catalytic substance selected from the group consisting of nickel on kieselguhr, zirconium-promoted cobalt, alumina- and calcium oxide-promoted iron oxide, molybdena, and nickel carbonate is present in an amount of about 5 percent by weight of said carbonaceous material.
5. The process of claim 1 wherein water is present in a ratio of up to about 1:5 with respect to said carbonaceous material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA358,743A CA1100532A (en) | 1980-08-21 | 1980-08-21 | Production of hydrocarbon liquids from solid carbonaceous materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA358,743A CA1100532A (en) | 1980-08-21 | 1980-08-21 | Production of hydrocarbon liquids from solid carbonaceous materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100532A true CA1100532A (en) | 1981-05-05 |
Family
ID=4117708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA358,743A Expired CA1100532A (en) | 1980-08-21 | 1980-08-21 | Production of hydrocarbon liquids from solid carbonaceous materials |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1100532A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618736A (en) * | 1980-12-18 | 1986-10-21 | Salford University Industrial Centre Limited | Conversion of a municipal waste to fuel |
| WO1988000935A1 (en) * | 1986-07-30 | 1988-02-11 | Whisenhunt, Fred, S. | Pyrolysis of biomass to produce maximum liquid yields |
| FR2605015A1 (en) * | 1986-10-10 | 1988-04-15 | Lyonnaise Eaux | PROCESS FOR TRANSFORMING WASTE CONTAINING ORGANIC MATTER. |
| US4982027A (en) * | 1986-01-24 | 1991-01-01 | Rheinische Braunkohlenwerke Ag | Process for the reprocessing of carbon containing wastes |
-
1980
- 1980-08-21 CA CA358,743A patent/CA1100532A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618736A (en) * | 1980-12-18 | 1986-10-21 | Salford University Industrial Centre Limited | Conversion of a municipal waste to fuel |
| US4982027A (en) * | 1986-01-24 | 1991-01-01 | Rheinische Braunkohlenwerke Ag | Process for the reprocessing of carbon containing wastes |
| WO1988000935A1 (en) * | 1986-07-30 | 1988-02-11 | Whisenhunt, Fred, S. | Pyrolysis of biomass to produce maximum liquid yields |
| FR2605015A1 (en) * | 1986-10-10 | 1988-04-15 | Lyonnaise Eaux | PROCESS FOR TRANSFORMING WASTE CONTAINING ORGANIC MATTER. |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |