US2057996A - Method for reducing organic substances - Google Patents
Method for reducing organic substances Download PDFInfo
- Publication number
- US2057996A US2057996A US431986A US43198630A US2057996A US 2057996 A US2057996 A US 2057996A US 431986 A US431986 A US 431986A US 43198630 A US43198630 A US 43198630A US 2057996 A US2057996 A US 2057996A
- Authority
- US
- United States
- Prior art keywords
- products
- organic substances
- water
- boiling
- reducing organic
- 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
- 238000000034 method Methods 0.000 title description 15
- 239000000126 substance Substances 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 238000009835 boiling Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- -1 terpene hydrocarbons Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- 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
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/929—Special chemical considerations
- Y10S585/943—Synthesis from methane or inorganic carbon source, e.g. coal
Definitions
- My invention relates to a method of reducing organic substances and more particularly phenols. It has particular reference to means whereby compounds of the phenol series including phenol proper as well as higher homologues thereof can easily be hydrogenated in the nucleus as well as" at the hydroxyl group. This method is in some way connected with the method of converting carbonaceous materials into liquidrioroducts, which is disclosed in my copending application -ior patent of the United States, Serial No.
- Thesecondensation products have a boiling point above 360 C. and are highly viscous. They can be used with great advantage as lubricants. Besides these condensation products there are formed considerable quantities of gaseous hydrocarbons, mainly methane.
- oils preferably such as are also hydrogenatable or such as are formed in the hydrogenation, for instance, tar oils and the hydrogenation products thereof.
- Example 1 Bituminous brown coal in finely ground condition, which may be mixed with an oil of high boiling point, is heated in an autoclave under continuous stirring with 50% by weight spongy iron and 50% water to 400-470".
- the carbon is recovered almost completely in liquid form, '20-30% ofa fraction boiling below 200 and 15-20% boiling between 200 and 300 being obtained.
- the products boiling above 200 C. contain about 12% tar acids.
- This latter fraction is subjected to. another treatment with water and spongy iron at 450-470 C. in the autoclave.
- the product obtained in this second operation is free from tar acids.
- On distillation about 12% were recovered as a fraction boiling below 180 C., while the rest had boiling points up to 350 C.
- the lower boiling fraction had a specific gravity of 0,78, the specific gravity of oil obtained in the first operation having amounted to about 0,9.
- Example 2 I there were recovered about 30-40% by weight (of the starting mixture) of hydrocarbons boiling up to 180 C. and having a specific gravity of about 0,8.
- the refractive index was about 1,45.
- the fractions boiling above 180 C. contain besides some cresols about 1020% or neutral hydrocarbons boiling up to 360 C.
- catalysts such as metallic nickel, iron, platinum, palladium orthe like.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
' "Patented 20, 193
PATENT OFFICE METHOD Fon REDUCING ORGANIC SUBSTANCES Richard Bayer, Bochum-Gerthe, Germany, as-
signor to Friedrich Uhd Application February 27, 1930,
N Drawing.
e, Dortmund, Germany Serial No. 431,986. In Germany March 6, 1929 GClaims. (Cl. 260-168) My invention relates to a method of reducing organic substances and more particularly phenols. It has particular reference to means whereby compounds of the phenol series including phenol proper as well as higher homologues thereof can easily be hydrogenated in the nucleus as well as" at the hydroxyl group. This method is in some way connected with the method of converting carbonaceous materials into liquidrioroducts, which is disclosed in my copending application -ior patent of the United States, Serial No.
394,393, which has matured into Patent 1,936,819, Nov. 28, 1933, and reference will be had to this process hereinafter. The present application is a continuation in part of Serial Number 394,393, now Patent 1,936,819, Nov. 28, 1933.
In the practice of the methods hitherto known for hydrogenating organic compounds under pressure and during decomposition,'such as the well known process disclosed by Bergius, which comprises treating carbon or its products of dis tillation with hydrogen supplied under pressure,
the phenols are not decomposed. On the other hand if these compounds are subjected to catalytic hydrogenation with metal. catalysts, such as nickel or nickel oxide, either at ordinary pressure according to Sabatier, or under higher pressure according to Ipatiew, compounds hydrogenated in the nucleus but still containing oxygen are obtained, which belong to the cyclohexanol yp I have now ascertained the surprising fact that pure phenol as well as its higher homologues resulting from the fractional distillation of tar; that is, phenolic bodies in general, canbe readily hydrogenated in the-nucleus as well as at-the hydroxyl group with the formation of" compounds of the cyclohexane type ((CH2)xwhich, in the case of the homologues, are related to the terpene hydrocarbons, if these compounds are treated with hydrogen developed during the decomposition under pressure by the reaction of finely divided metals, and more especially iron and water.
If this method is applied to phenol profier, secondary reactions leading to condensation products will occur. Thesecondensation products have a boiling point above 360 C. and are highly viscous. They can be used with great advantage as lubricants. Besides these condensation products there are formed considerable quantities of gaseous hydrocarbons, mainly methane.
' I have further found that these secondary reactions can be prevented from occurring: if,
other oils, preferably such as are also hydrogenatable or such as are formed in the hydrogenation, for instance, tar oils and the hydrogenation products thereof.
In this manner it is, for instance, possible to completely convert tarry products, such as the tar acids, etc., which were formed when sub- 'ecting carbonaceous material, such as brown coal or brown coal producer tar with afinely divided metal and water to the combined action of heatand high pressure, as disclosed in my copending application aforesaid, into neutral oils insoluble in alkalis. The'quantity. of hydrogenated products obtained in this second operation corresponds to the quantity of oxygen containing compounds.
In practicing my invention I'may, for instance, proceed as follows:
Example 1 Bituminous brown coal in finely ground condition, which may be mixed with an oil of high boiling point, is heated in an autoclave under continuous stirring with 50% by weight spongy iron and 50% water to 400-470". The carbon is recovered almost completely in liquid form, '20-30% ofa fraction boiling below 200 and 15-20% boiling between 200 and 300 being obtained. The products boiling above 200 C. contain about 12% tar acids. This latter fraction is subjected to. another treatment with water and spongy iron at 450-470 C. in the autoclave. The product obtained in this second operation is free from tar acids. On distillation about 12% were recovered as a fraction boiling below 180 C., while the rest had boiling points up to 350 C. The lower boiling fraction had a specific gravity of 0,78, the specific gravity of oil obtained in the first operation having amounted to about 0,9.
Example 2 I there were recovered about 30-40% by weight (of the starting mixture) of hydrocarbons boiling up to 180 C. and having a specific gravity of about 0,8. The refractive index was about 1,45. The fractions boiling above 180 C. contain besides some cresols about 1020% or neutral hydrocarbons boiling up to 360 C.
The products hydrogenated in the nucleus,
which are obtained in the reaction, can be converted into aromatic hydrocarbons by dehydrogenation with catalysts, such as metallic nickel, iron, platinum, palladium orthe like.
Various changes may be made in the details disclosed in the foregoing specification without departing from the invention or sacrificing the advantages thereof.
In the claims aflixed to this specification no selection of any particular modification of the invention is intended to the exclusion of other modifications thereof and the right to subsequently make claim to any modification not covered by these claims is expressly reserved.
I claim:--
1. The process of hydrogenating phenol and its homologues which comprises subjecting a mixture of such a compound with liquid water and with a finely divided metal capable of reacting with the water to form hydrogen at temperatures of the order of 400 C., to high temperatures of at least about 400 C. and to high pressures developed autogenously within a closed reaction chamber.
2. The process of hydrogenating phenol and its homologues which comprises subjecting a mixture of such a compound with liquid water and with finely divided iron to temperatures ranging between about 400 to 470 C. and to pressures developed autogenously within a closed reaction vessel.
3. In the reduction of phenol and its homologues, the process which comprises mixing such a compound with a quantity of liquid water and of spongy iron suflicient to produce enough hydrogen to reduce said body and subjecting this mixture to temperatures of the order of 400 to 470 C. and to pressures developed autogenously.
4. In the production of liquid hydrocarbon products from carbonaceous materials, the process which comprises subjecting such a material to the action of water and spongy iron at temperatures of the order of 400 to 470 C. and to pressures developed autogenously, separating a phenol-containing fraction from the reaction products, subjecting said fraction to a second similar treatment with water and spongy iron, and recovering the liquid hydrocarbon products thereby produced.
5. The process of claim 4 in which the carbonaceous material is mixed with an oil prior to treatment.
6. In the reduction of phenols, the process which comprises mixing a carbonaceous material containing phenols with about to per cent of spongy iron and about 20 to 50 per cent of water, heating the mixture in an enclosed chamber to temperatures of the order of 400 to 470 C. and recovering the liquid products thereby produced.
RICHARD BAYER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2057996X | 1929-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2057996A true US2057996A (en) | 1936-10-20 |
Family
ID=7982968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US431986A Expired - Lifetime US2057996A (en) | 1929-03-06 | 1930-02-27 | Method for reducing organic substances |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2057996A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2547274A (en) * | 1948-11-17 | 1951-04-03 | Universal Oil Prod Co | Partial hydrogenation of unsaturated conjunct polymer hydrocarbons |
| US2739929A (en) * | 1951-08-24 | 1956-03-27 | Texas Co | Recovery of catalyst in the hydrogenation of hydrocarbon oils |
| US3930984A (en) * | 1970-10-01 | 1976-01-06 | Phillips Petroleum Company | Coal-anthracene oil slurry liquefied with carbon monoxide and barium-promoted catalysts |
-
1930
- 1930-02-27 US US431986A patent/US2057996A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2547274A (en) * | 1948-11-17 | 1951-04-03 | Universal Oil Prod Co | Partial hydrogenation of unsaturated conjunct polymer hydrocarbons |
| US2739929A (en) * | 1951-08-24 | 1956-03-27 | Texas Co | Recovery of catalyst in the hydrogenation of hydrocarbon oils |
| US3930984A (en) * | 1970-10-01 | 1976-01-06 | Phillips Petroleum Company | Coal-anthracene oil slurry liquefied with carbon monoxide and barium-promoted catalysts |
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