US2278407A - Thermal treatment of carbonaceous materials - Google Patents
Thermal treatment of carbonaceous materials Download PDFInfo
- Publication number
- US2278407A US2278407A US384742A US38474241A US2278407A US 2278407 A US2278407 A US 2278407A US 384742 A US384742 A US 384742A US 38474241 A US38474241 A US 38474241A US 2278407 A US2278407 A US 2278407A
- Authority
- US
- United States
- Prior art keywords
- thermal treatment
- carbonaceous materials
- metals
- metal
- catalyst
- 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
- 238000007669 thermal treatment Methods 0.000 title description 8
- 239000003575 carbonaceous material Substances 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 230000001066 destructive effect Effects 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
Definitions
- the present invention relates to the thermal treatment of carbonaceous materials.
- mixtures have up to the present generally been produced by co-precipitation from aqueous solutions of salts of the said metals or by sulphidizing a mixture of the metals or metal compounds or a compound containing both metals, for example nickel tungstate.
- hydrocarbon oils can be produced from carbonaceous materials with advantage by thermal treatment, for instance by treating with hydrogen or gases containing hydrogen or by cracking, in contact with catalysts, if as catalysts are used mixtures of metal sulphides, which have been obtained-by mixing in a dry state ammonium thio-salts of metals of the 6th group of the periodic system with finelydivided metals of the iron group obtained from the corresponding carbonyl compounds, and heating the mixture, if desired after grinding it, at temperatures above 300 C.,
- ammonium thio-' molybdates or tungstates are preferably employed as ammonium thio-salts of the metals of to the total catalyst.
- Other percentages for the components, however, may also be employed, for example such in which the metals of theiron group are given preponderance.
- the dry mixture of thio-salt and metalafter being ground, if desired, is then heated to temperatures of from 300' to 500 0., preferably from 375 to 475 C., for example for from 1 to 24 hours. This is best achieved in a current of a gas containing hydrogen, carbon dioxide or nitrogen or more than one of these-gases.
- the efltciency of the catalyst is increased by carrying out the heating with the addition'of a sulphurizing medium, as for example hydrogen sulphide.
- the said hydrogenationv processes are as a rille 7 carried out at temperatures of between 300 and 600 C. and in practice between about 380". and 480 C, and under high pressures of at least 50 atmospheres, for example 100, 200, 300, 700 or 1000 atmospheres or more.
- the catalysts according to the present invention are also particularly suitable for the hydrogenation of polymerization products, such as for the 6th group which may, for example, be produced by dissolving molybdicor tungstic acid in a solution of ammonium sulphide and introducing hydrogen sulphide.
- the thio-salts so obtained are then separated, dried and mixed with iron, nickel or cobalt produced in a finely dispersed state by decomposing the corresponding metal carbonyls at a high temperature in.known manner.
- the metals of the iron group are employed inan amount of from 1 to 50 per cent, preferably from 1 to 30 per cent, advantageously from 5 to 25 per cent, calculated with reference example the hydrogenation of diisobutylene for the manufacture of isooctane.
- Example 1 atomic proportion of nickel prepared by the thermal decomposition of nickel carbonyl is intimately mixed with 2 molecular proportions of ammonium thiotungstate in a ball mill and treated in a current of hydrogen at from 400 to 450 C. for 2 to 3 hours until the evolution of ammonia subsides.
- the powder is cooled in the obtained a pressure of 50 atmospheres at a temperature of 485 C. the throughput being adjusted to 0.5 kilogram oi initial material per liter of catalyst space per ho while the amount of hydrogen is 2 cubic meters per kilogram of initial material per hour.
- a gasoline is obtained containing 57 per cent of aromatic hydrocarbons.
- thermo treatment is a destructive hydrogenation under a pressure of at least 50 atmospheres.
- a process for the production of hydrocarbons of lower boiling point from hydrocarbons of higher boiling point by cracking in the presence of a catalyst which comprises using as catalyst a mixture of metal sulphides, which has been obtained by mixing in a dry state an ammonium thio-salt of a metal of the 6th group or the periodic system, with a finely divided metal of the iron group obtained from the corresponding carbonyl compound and. heating the mixture at temperatures above300 C., at least until the formation 01' ammonia ceases.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
m ma Apr. 194g 2.21am j THERMAL TREATMENT or cannomcsous m Anthea, Wilhelm v. l-uener m Walter Simon, Ludwigshafen-on-thclhine, Germany,
allignorstol.
nlndustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany x; 1mm. Application much 22, 1941, Serial No. 384,742. Germany April 1040 9'Olalms. (CL 196-52) The present invention relates to the thermal treatment of carbonaceous materials.
It is already known to carry out the destructive hydrogenation under pressure or the cracking of carbonaceous materials in contact with catalysts comprising metal sulphides, especially heavy metal sulphides, for example those produced by heating the corresponding thio-salts. It has further been proposed to use mixtures of sulphides of the metals of the 6th group of the periodic system (more particularly molybdenum or tungsten) with sulphides of the metals of the iron group (iron, nickel or cobalt) for this purpose. These mixtures have up to the present generally been produced by co-precipitation from aqueous solutions of salts of the said metals or by sulphidizing a mixture of the metals or metal compounds or a compound containing both metals, for example nickel tungstate.
We have now found that valuable hydrocarbon oils can be produced from carbonaceous materials with advantage by thermal treatment, for instance by treating with hydrogen or gases containing hydrogen or by cracking, in contact with catalysts, if as catalysts are used mixtures of metal sulphides, which have been obtained-by mixing in a dry state ammonium thio-salts of metals of the 6th group of the periodic system with finelydivided metals of the iron group obtained from the corresponding carbonyl compounds, and heating the mixture, if desired after grinding it, at temperatures above 300 C.,
preferably in the presence of reducing or inert gases. Heating is preferably continued until the evolution of ammonia subsides. This method of tained so that economies are realized in the said hydrocarbon production.
For preparing the catalyst ammonium thio-' molybdates or tungstates are preferably employed as ammonium thio-salts of the metals of to the total catalyst. Other percentages for the components, however, may also be employed, for example such in which the metals of theiron group are given preponderance.
The dry mixture of thio-salt and metalafter being ground, if desired, is then heated to temperatures of from 300' to 500 0., preferably from 375 to 475 C., for example for from 1 to 24 hours. This is best achieved in a current of a gas containing hydrogen, carbon dioxide or nitrogen or more than one of these-gases. The efltciency of the catalyst is increased by carrying out the heating with the addition'of a sulphurizing medium, as for example hydrogen sulphide.
The thermal treatment with hydrogen or gases containing hydrogen, in the presence of catalysts according to the process of the present invention,
may comprise, for example simple hydrogenation or destructive hydrogenation processes and also dehydrogenation processes.
The said hydrogenationv processes are as a rille 7 carried out at temperatures of between 300 and 600 C. and in practice between about 380". and 480 C, and under high pressures of at least 50 atmospheres, for example 100, 200, 300, 700 or 1000 atmospheres or more.
The catalysts according to the present invention are also particularly suitable for the hydrogenation of polymerization products, such as for the 6th group which may, for example, be produced by dissolving molybdicor tungstic acid in a solution of ammonium sulphide and introducing hydrogen sulphide. The thio-salts so obtained are then separated, dried and mixed with iron, nickel or cobalt produced in a finely dispersed state by decomposing the corresponding metal carbonyls at a high temperature in.known manner. The metals of the iron group are employed inan amount of from 1 to 50 per cent, preferably from 1 to 30 per cent, advantageously from 5 to 25 per cent, calculated with reference example the hydrogenation of diisobutylene for the manufacture of isooctane.
The following example will further illustrate the nature of our said invention and how the same can be carried out in practice, but it should he understood that the invention is not limited to the said example.
Example 1 atomic proportion of nickel prepared by the thermal decomposition of nickel carbonyl is intimately mixed with 2 molecular proportions of ammonium thiotungstate in a ball mill and treated in a current of hydrogen at from 400 to 450 C. for 2 to 3 hours until the evolution of ammonia subsides. The powder is cooled in the obtained a pressure of 50 atmospheres at a temperature of 485 C. the throughput being adjusted to 0.5 kilogram oi initial material per liter of catalyst space per ho while the amount of hydrogen is 2 cubic meters per kilogram of initial material per hour. A gasoline is obtained containing 57 per cent of aromatic hydrocarbons.
what we claim is:
1. A process for the production of hydrocarbons from a carbonaceous material by thermal treatment at temperatures 01 between 300 and 600 C., in the presence of a catalyst, which comprises using as catalyst a mixture of metal sulphides, which has been obtained by mixing ina dry state an ammonium thio-salt or a metal of the 6th group of the periodic system with a finely divided metal of the iron group obtained from the corresponding carbonyl compound, and heating the mixture at temperatures above 300 C.
2. A process as claimed in claim 1, which comprises heating the dry mixture in the presence of treatment at temperatures of .between 300 and 600 C. in the presence or hydrogen in the presence of a catalyst, which comprises using as catalyst a mixture of metal sulphides, which has been obtained by mixing in a dry state an am-' monium thio-salt or a metal 01' the 6th group or the periodic system, with a finely divided metal or the iron group obtained from the corresponding carbonyl compound and heating the mixture at temperatures above 300' C., at least until the formation of ammonia ceases.
'7. A process as claimed in claim 6, wherein the thermal treatment is a destructive hydrogenation under a pressure of at least 50 atmospheres.
8.v A process as claimed in claim 6, wherein the thermal treatment is a dehydrogenation under v pressure.
9. A process for the production of hydrocarbons of lower boiling point from hydrocarbons of higher boiling point by cracking in the presence of a catalyst, which comprises using as catalyst a mixture of metal sulphides, which has been obtained by mixing in a dry state an ammonium thio-salt of a metal of the 6th group or the periodic system, with a finely divided metal of the iron group obtained from the corresponding carbonyl compound and. heating the mixture at temperatures above300 C., at least until the formation 01' ammonia ceases. 1
, EUGEN ANTHES.
. WILHELM v. FUENER. WALTER SIMON.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2278407X | 1940-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2278407A true US2278407A (en) | 1942-04-07 |
Family
ID=7993467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US384742A Expired - Lifetime US2278407A (en) | 1940-04-05 | 1941-03-22 | Thermal treatment of carbonaceous materials |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2278407A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2554282A (en) * | 1946-09-12 | 1951-05-22 | Standard Oil Dev Co | Lubricating oil manufacture |
| US2709151A (en) * | 1950-12-01 | 1955-05-24 | Basf Ag | Process for the recovery of gasoline from petroleum oils or crude residues by destructive hydrogenation with the use of a catalyst |
| US2809219A (en) * | 1952-06-16 | 1957-10-08 | Inventa Ag | Process for hydrolyzing sulfite waste liquor |
-
1941
- 1941-03-22 US US384742A patent/US2278407A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2554282A (en) * | 1946-09-12 | 1951-05-22 | Standard Oil Dev Co | Lubricating oil manufacture |
| US2709151A (en) * | 1950-12-01 | 1955-05-24 | Basf Ag | Process for the recovery of gasoline from petroleum oils or crude residues by destructive hydrogenation with the use of a catalyst |
| US2809219A (en) * | 1952-06-16 | 1957-10-08 | Inventa Ag | Process for hydrolyzing sulfite waste liquor |
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