US1904477A - Production of valuable organic products - Google Patents
Production of valuable organic products Download PDFInfo
- Publication number
- US1904477A US1904477A US244769A US24476928A US1904477A US 1904477 A US1904477 A US 1904477A US 244769 A US244769 A US 244769A US 24476928 A US24476928 A US 24476928A US 1904477 A US1904477 A US 1904477A
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- Prior art keywords
- oils
- pressure
- coal
- production
- products
- Prior art date
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- Expired - Lifetime
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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
- C10G1/08—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
-
- 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
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
- C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S208/00—Mineral oils: processes and products
- Y10S208/951—Solid feed treatment with a gas other than air, hydrogen or steam
Definitions
- solid carbonaceous initial materials may be employed according to the process as for exam%le diiferent'kinds of coal, such as it coal or rown coal of varied origin and c aracter, as well as bituminous shales, peat, wood and the like.
- vIt may also be advantageous to c315? e the operation in several stages at out.
- the temperature may also vary and, as a rule,'higher temperatures give higher yields of liquid products. Temperatures of between 300 and 400 C. are preferably employed, An upper temperature limit is set by the critical temperatureof the added liquid hydrocarbons and the. like, but the temperatures must not be so high that the added oils. are changed in such a manner that they lose their properties as triturating agents for thecoal and the like.
- the heat may be supplied in difierent ways :
- the mixture of coal and triturating agents which ifdesired, may be -'preheated, is heated externally during the process intubes, for example coils.
- Superheating is preferably avoided, for example by the employment of a bath (for instance a salt bath or a metallic melt) or of hot gases as heating medium.
- the heat may also be produced electrically, for example by heating. the tubes or coils themselves electrically or by arranging fixed or movable ele'ctric'resiste ances in the tubes.
- Stirrers may also be em- I ployed, and if desired, thesemayalso be con- 75 structed as electric resistance heating devices.
- W'e may also work in such amanner that the pasty mass is preheated'up to about the ,reaction temperature and that the heat necessary to carry out the process is introducedby means of heat conveying'media," for example a gas or a liquid, whichv may be allowed to circulate round thereaction vessel or may be introduced into the'reaction cham-.
- heat conveying'media for example a gas or a liquid, whichv may be allowed to circulate round thereaction vessel or may be introduced into the'reaction cham-.
- the process may also be carried out in such a manner that. part of the added-hydrocarbons for instance are heated above the temperature of the reaction and are employedas heat-conveying media.
- the method of heat sup may "also be combined with-one of the a orementioned methods.
- reaction products are cooled down behind 'the reaction space so far that part I as the treatment of fresh coal or the like; or I they may be subjected after the extraction has been carried as far as possible to a treatment with hydrogen with or without the application of pressure and if desired with catalysts, before the solid components have been separated oif and in this way substances of the nature of middle oils, benzines and the. like are obtained.
- the solid residue may, for example by treatment with hydrogen under pressure, be employed for the production of valuble hydrocarbons and the like. Under certain circumstances it mayalso be advantageous to release the pressure while the products are still hot and then to cool under normal pressure.
- the liquid products are separated from r the solid residues in any known and convenient manner as for example by low temperature carbonization, if desired in the presence of steam or other gases and vapors, or by extraction or' both, or by other means with or without the application of pressure.
- reaction product or components of the same may also be subjected to cracking in the presence or absence of water vapor or carbon dioxid or other gases.
- oils which may be added mixtures boiling within a rather wide range of temperatures come into question. They may be obtained in various ways, for example by the distillation or low temperature carbonization of lignite or coal or from mineral oils or by the destructive hydrogenation of substances of the nature of coal, tars, mineral oils and the like or bythe catalytic reduction of oxids of carbon with hydrogen under pressure. Fractions of oils which are produced in the present process itself and boil above the boiling point range of benzine, namely above about 180 C. are very suitable. Mixtures of such oils with oils boiling above 300 C. may also be employed with advantage, but also homogeneous substances or groups of substances may be employed, forexample xylene, cresol, hydrogenated naphthalenes, aniline and the like.
- a is a ho per through terials can be introduced into a mixing vessel p; b is a pipe for the introduction of solvent hydrocarbons into the said vessel p. c is a stirrer which 'isfactuated by rotation of the wheel 0 the rotation being transferred by means of the tooth gear m to the shaft n. d is-a pipe for the transference of the liquid mixtures prepared in the vessel 12 to the pres--' sure resistant coil' f which is constructed of sure release valve for releasing the pressure on the said products.
- Example 1 Brown coal containing about 3 per cent of bitumen (that is to say substances which can be extracted by means of benzene) and 5 to 10 per cent of water is treatedat about 350 C. with those fractions of oils boiling between 190 and 250 C. derived from the destructive hydrogenation of carbonaceous substances at a pressure of 200 atmospheres. 60 to 70 per cent of the coal is converted in a rapid process, without an appreciable amount of-gas being formed, into liquid oils, whereas at a pressure of 50 atmospheres under otherwise like conditionsonly about half that amount would be obtained.
- bitumen that is to say substances which can be extracted by means of benzene
- Example 2 Brown coal triturated with xyleneis passed through a high pressure coil heated to about between 320 and 340 C. at a pressure of 200 atmospheres. On releasing the pressure,
Description
April 1933- c. KRAUCH ET AL PRODUCTION OF VALUABLE ORGANIC PRODUOTS Filed Jan. 5, 1928 "ORNEYS Patented A1. is, 1933 UNITED s'ra'ras PATENT o-Fncs CAB'L KBAUCH, OF LUDWIGSHAFEN-ON-TH E-IBIHITN'IE; MATHIAS PIER, OF HEIDELBEBG,
.ELNID EUGEN ANTQHES, OF 13TH) FIIIGtSHAFIIilN-011'.-'I.IHIE-BHIIIE, GERMANY, ASSIGNORS TO I. G. FABBENINDUSTRIE AKTIENGESELLSCHAFT, OF FRANKFORT ON-THE-MAIN, GERMANY, A. COBPORATION OF GERMANY PRODUCTION OF VALUAIBLE ORGANIC PIBDDUOTS Application filed January 5, 1928, Serial No This invention relates to the production of valuable organic products from solid carbonaceous initial materials;
We have found that an excellent yield of 5 liquid products and products which liquefy when heated and which are hereinafter referred to for the sake of brevity as valuable hydrocarbon products, is obtained by treating solid carbonaceous materials with such hydrocarbons as are liquid under the-conditions of the reaction, substantially free from components boiling below 100. C. and which mainly boil between 100 and 300 C. under elevated pressures of at least 75 atmospheres, but preferably 100 atmospheres or above, at temperatures below the'coking temperature of the added hydrocarbons and in the. absence of substantial amounts of hydro en. B this manner of proceeding the forma ion o gases and especially such as condense with difliculty is prevented to a large extent.
A great variety of solid carbonaceous initial materials may be employed according to the process as for exam%le diiferent'kinds of coal, such as it coal or rown coal of varied origin and c aracter, as well as bituminous shales, peat, wood and the like.
Ifdesired, ases substantially free from-hydrogen such or example as nitrogen, carbon L dioxid, carbon monoxid, or gas mixtures containin the same may also be employed, and an ad tion of catalytic substances which may have a decomposing action on coal, such for example as. iodine or other 'me'talloid's or sub.-
stances with an alkaline reaction, in particular the sulfids ofthe alkali metals and alkaline earth metals, also proves useful.
vIt may also be advantageous to c315? e the operation in several stages at out. rent '40 pressures 'for example, the initial material maybe pretreated first at a pressure which may ,be below 7 5 atmospheres and'then the product thus obtained treated at higher pressures according to the process above described. We may, however, also commence with higher presures and then vary the pressure withinwide limits during the process. I Pressures of 200 atmospheres and more, for
- example of 1000 atmospheresmay employed.
. 244,768, and in Germany January 13, 19 7.
v The temperature may also vary and, as a rule,'higher temperatures give higher yields of liquid products. Temperatures of between 300 and 400 C. are preferably employed, An upper temperature limit is set by the critical temperatureof the added liquid hydrocarbons and the. like, but the temperatures must not be so high that the added oils. are changed in such a manner that they lose their properties as triturating agents for thecoal and the like.
The heat may be supplied in difierent ways :For example, the mixture of coal and triturating agents, which ifdesired, may be -'preheated, is heated externally during the process intubes, for example coils. Superheating is preferably avoided, for example by the employment of a bath (for instance a salt bath or a metallic melt) or of hot gases as heating medium. The heat may also be produced electrically, for example by heating. the tubes or coils themselves electrically or by arranging fixed or movable ele'ctric'resiste ances in the tubes. Stirrers may also be em- I ployed, and if desired, thesemayalso be con- 75 structed as electric resistance heating devices.
W'e may also work in such amanner that the pasty mass is preheated'up to about the ,reaction temperature and that the heat necessary to carry out the process is introducedby means of heat conveying'media," for example a gas or a liquid, whichv may be allowed to circulate round thereaction vessel or may be introduced into the'reaction cham-.
her at a suitablepoint; The process" may also be carried out in such a manner that. part of the added-hydrocarbons for instance are heated above the temperature of the reaction and are employedas heat-conveying media. The method of heat sup ly may "also be combined with-one of the a orementioned methods.
The reaction products are cooled down behind 'the reaction space so far that part I as the treatment of fresh coal or the like; or I they may be subjected after the extraction has been carried as far as possible to a treatment with hydrogen with or without the application of pressure and if desired with catalysts, before the solid components have been separated oif and in this way substances of the nature of middle oils, benzines and the. like are obtained. Also the solid residue may, for example by treatment with hydrogen under pressure, be employed for the production of valuble hydrocarbons and the like. Under certain circumstances it mayalso be advantageous to release the pressure while the products are still hot and then to cool under normal pressure. After being subjected if required to a preliminary mechanical treatment such as centrifuging and the like the liquid products are separated from r the solid residues in any known and convenient manner as for example by low temperature carbonization, if desired in the presence of steam or other gases and vapors, or by extraction or' both, or by other means with or without the application of pressure.
The reaction product or components of the same may also be subjected to cracking in the presence or absence of water vapor or carbon dioxid or other gases.
As substances which may be added, mixtures boiling within a rather wide range of temperatures come into question. They may be obtained in various ways, for example by the distillation or low temperature carbonization of lignite or coal or from mineral oils or by the destructive hydrogenation of substances of the nature of coal, tars, mineral oils and the like or bythe catalytic reduction of oxids of carbon with hydrogen under pressure. Fractions of oils which are produced in the present process itself and boil above the boiling point range of benzine, namely above about 180 C. are very suitable. Mixtures of such oils with oils boiling above 300 C. may also be employed with advantage, but also homogeneous substances or groups of substances may be employed, forexample xylene, cresol, hydrogenated naphthalenes, aniline and the like.
The invention will bexfurther illustrated with reference to the accompanying drawing in which a plant for carrying out the process according to the present invention is illustrated diagrammatically, partly in vertical cross section, although the invention is not which finely divided solid car onaceous ma-.
limited thereto. a is a ho per through terials can be introduced into a mixing vessel p; b is a pipe for the introduction of solvent hydrocarbons into the said vessel p. c is a stirrer which 'isfactuated by rotation of the wheel 0 the rotation being transferred by means of the tooth gear m to the shaft n. d is-a pipe for the transference of the liquid mixtures prepared in the vessel 12 to the pres--' sure resistant coil' f which is constructed of sure release valve for releasing the pressure on the said products. It is a settling tank from which the li uid products can be removed by, means 0 the pipe is, whereas the solid mixtures are removed by means of the p p Referring to the accompanying drawing finely divided coal rich in gas is mixed in the vessel p, which is fitted with the stirrer 0 withlthe fractions boiling between and 300 C. of a crude mineral oil, both constituents of the mixture being continuously introduced. The paste thusobtained is continuously passed to the compression pump a and is forced under a pressure of 200 atniospheres into a pressure-resistant coil 7 constructed of alloy steels which is maintained at a temperature of about 320 C. The
products issuing from the said coil are cooled.
Example 1 Brown coal containing about 3 per cent of bitumen (that is to say substances which can be extracted by means of benzene) and 5 to 10 per cent of water is treatedat about 350 C. with those fractions of oils boiling between 190 and 250 C. derived from the destructive hydrogenation of carbonaceous substances at a pressure of 200 atmospheres. 60 to 70 per cent of the coal is converted in a rapid process, without an appreciable amount of-gas being formed, into liquid oils, whereas at a pressure of 50 atmospheres under otherwise like conditionsonly about half that amount would be obtained.
Example 2 Brown coal triturated with xyleneis passed through a high pressure coil heated to about between 320 and 340 C. at a pressure of 200 atmospheres. On releasing the pressure,
over 50 per 'cent of the coal is obtained as liquid oils by means of centrifuging followed by extraction or steam distillation.
What we claim is:
1. Theprocess of extracting oils of about the viscosity of lubricating oils from solid non-asphaltic pyrobituminous materials by passing said solid materials through a reaction zone, while treating said materials with a substance of the nature of tar oils, the-major" portion of the constituents of which boil between 100 C. and 300 C. and a sul hide selected from the class of t e a1-. kali metal and alkaline earthmetal sul hides set our hands.
ata temperature of from 300 and 9. pressure of at least 75 atmospheres, so rapidly that no low boiling ydrocarbons are produced, then directly cooling the reaction mixture to separate out solid materials item the liquids having a viscosity of about that of lubricating oils;
-2. A process as defined in claim 1 wherein the pyrobituminous material. is brown and the substance of the nature of tar'oils is xylene. 1
3. The process of extracting oils of about the viscosity of lubricating'oils from solid, non-asphaltic, yro-bituminous materials by passing said so 1d materials through a reaction zone while treating them with a hydrocarbon liquid, the major constituents'of which boil between 100 and 300 C. -at..a tem ture of'from 300 to 400 andv un er a pressure of at least 75 atm heres, until at least 50% of the oil contain in said initial material is extracted therefrom but for only so long that substantially no low boiling 11y: drocarbons are produced, said hydrocarbon liquld being maintained. in the liquid state throughout the process, and then-separa the liquid extraction from the residual soli materials. V
In testimony whereof wehave hereunto CARL moon. m'rmas PIER. EUGENANTHES.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1904477X | 1927-01-13 |
Publications (1)
Publication Number | Publication Date |
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US1904477A true US1904477A (en) | 1933-04-18 |
Family
ID=7748581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US244769A Expired - Lifetime US1904477A (en) | 1927-01-13 | 1928-01-05 | Production of valuable organic products |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2665238A (en) * | 1951-07-12 | 1954-01-05 | Texas Co | Recovery of oil from shale |
US2714086A (en) * | 1951-03-06 | 1955-07-26 | Bluemner Erwin | Chemical modification of coal into hydrocarbon oils and coke |
US2913388A (en) * | 1954-11-30 | 1959-11-17 | John H Howell | Coal hydrogenation process |
US4536279A (en) * | 1984-01-19 | 1985-08-20 | Mobil Oil Corporation | Enhanced recovery of hydrocarbonaceous fluids from oil shale |
-
1928
- 1928-01-05 US US244769A patent/US1904477A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2714086A (en) * | 1951-03-06 | 1955-07-26 | Bluemner Erwin | Chemical modification of coal into hydrocarbon oils and coke |
US2665238A (en) * | 1951-07-12 | 1954-01-05 | Texas Co | Recovery of oil from shale |
US2913388A (en) * | 1954-11-30 | 1959-11-17 | John H Howell | Coal hydrogenation process |
US4536279A (en) * | 1984-01-19 | 1985-08-20 | Mobil Oil Corporation | Enhanced recovery of hydrocarbonaceous fluids from oil shale |
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