DE183856C - - Google Patents
Info
- Publication number
- DE183856C DE183856C DENDAT183856D DE183856DA DE183856C DE 183856 C DE183856 C DE 183856C DE NDAT183856 D DENDAT183856 D DE NDAT183856D DE 183856D A DE183856D A DE 183856DA DE 183856 C DE183856 C DE 183856C
- Authority
- DE
- Germany
- Prior art keywords
- formic acid
- formaldehyde
- tin
- paraformaldehyde
- oxide
- 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.)
- Active
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 28
- 235000019253 formic acid Nutrition 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N Methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- PTSNAAXZLFGCNO-UHFFFAOYSA-N formic acid;tin Chemical compound [Sn].OC=O PTSNAAXZLFGCNO-UHFFFAOYSA-N 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000015450 Tilia cordata Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001809 detectable Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- -1 formic acid compound Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
Description
KAISERLICHES PATENTAMT.IMPERIAL PATENT OFFICE.
Es ist bekannt, daß man die Aldehyde der Fettsäuren durch trockene Destillation eines Gemenges ihrer Kalk- oder Barytsalze mit ameisensaurem Kalk darstellen kann. Nur der Aldehyd der Ameisensäure macht von dieser sonst allgemein gültigen Regel eine Ausnahme. Ameisensaure Erden oder ameisensaure Alkalien geben bei trockener Destillation nur äußerst geringe Mengen Formaldehyd. Solche äußerst geringe Mengen Formaldehyd sind zwar sowohl durch den Geruch als auch durch den Silberspiegel und durch sonstige besonders empfindliche Aldehydreaktionen nachweisbar, lassen aber an eine technische Verwertung nicht denken. Man erhält eben nachweisbare Mengen von Formaldehyd auch, wie nunmehr gefunden wurde, bei der trockenen Destillation der meisten Ameisensäuresalze, insbesondere des Eisensalzes.It is known that the aldehydes of the fatty acids by dry distillation of a Can represent a mixture of their lime or barite salts with formic acid lime. Just the aldehyde of formic acid constitutes one of this otherwise generally applicable rule Exception. Formic acid earths or formic acid alkalis give with dry distillation only extremely small amounts of formaldehyde. Such extremely small amounts of formaldehyde are through both the smell and the silver mirror and through other particularly sensitive aldehyde reactions detectable, but leave a technical one Do not think of recovery. Detectable amounts of formaldehyde are also obtained, as has now been found in the dry distillation of most formic acid salts, especially the iron salt.
ao Der Grund dafür, daß die Ausbeute an Formaldehyd so gering ist, ist wohl darin zu suchen, daß der Aldehyd bei dieser Darstellungsweise erst bei einer Temperatur gebildet werden kann, die oberhalb seiner Zer-Setzungstemperatur liegt. Gelingt es, eine Ameisensäureverbindung zu finden, deren Zersetzung schon bei einer wesentlich niedrigeren Temperatur stattfindet,, dann darf erwartet werden, daß auch die Ausbeute an Formaldehyd reichlicher sein wird.ao The reason why the yield of formaldehyde is so low is probably because of this to look for the fact that the aldehyde is only formed at one temperature in this mode of presentation which is above its decomposition temperature. If a formic acid compound is found, its decomposition already takes place at a much lower temperature, then may be expected that the yield of formaldehyde will also be more abundant.
Es wurde nun gefunden, daß ameisensaures Zinn sich schon bei mäßiger Erwärmung, etwa bei 1800G., in Oxyd oder Oxydul, Formaldehyd und Kohlensäure zersetzt. Der.It has now been found that ants acidic tin decomposes even at moderate heating, for example at 180 0 G., into oxide or ferrous oxide, formaldehyde and carbon dioxide. Of the.
entstehende Formaldehyd tritt nur zum geringsten Teil als solcher auf, vielmehr hauptsächlich als Paraformaldehyd. Dieser läßt sich leicht als Sublimationsprodukt niederschlagen. Geringe Anteile an gewöhnlichem gasförmigen Aldehyd, die zugleich entstehen, können durch geeignete Lösungsmittel festgehalten werden.The formaldehyde produced occurs only to a small extent as such, rather mainly as paraformaldehyde. This can easily be deposited as a sublimation product. Small proportions of common gaseous aldehyde, which are formed at the same time, can be held in place by suitable solvents will.
Trägt man dafür Sorge, daß eine stärkere Abkühlung der entstehenden flüchtigen Produkte stattfindet, so beobachtet man außerdem noch die Kondensation einer beträchtlichen Menge von Ameisensäuremethyläther in flüssigem Zustande.Care should be taken to ensure that the volatile products formed are cooled down more strongly takes place, one also observes the condensation of a considerable amount Amount of formic acid methyl ether in a liquid state.
Zur Erklärung dieser Erscheinung mag darauf aufmerksam gemacht werden, daß Paraformaldehyd nach den heutigen Anschauungen als aus wenigstens drei Molekülen Formaldehyd kondensiert betrachtet wird. Ameisensäuremethyläther kann vielleicht als aus zwei Molekülen Formaldehyd entstanden gedacht werden:To explain this phenomenon it should be pointed out that Paraformaldehyde, according to today's point of view, consists of at least three molecules Formaldehyde is considered condensed. Formic acid methyl ether may can be thought of as originating from two molecules of formaldehyde:
2HCOH2HCOH
C HO · C O - H. C HO CO - H.
Die Gesamtheit der hier in Betracht kommenden Vorgänge würde dann etwa durch folgende Gleichung veranschaulicht werden können:The entirety of the processes under consideration here would then approximately go through the following equation can be illustrated:
Sn(HCOO)^ ameisensaures Zinn Sn (HCOO) ^ formic acid tin
kann gebencan give
SnOSnO
ZinnoxydulTin oxide
CO2 CO 2
Kohlensäurecarbonic acid
6565
(HCOH)x (HCOH) x
Formaldehyd, Paraformaldehyd, Ameisensäuremethyläther. Formaldehyde, paraformaldehyde, formic acid methyl ether.
Statt von fertig gebildetem ameisensauren Zinn auszugehen, kann man auch in der Weise verfahren, daß man Ameisensäure (Dampf) über mäßig erhitztes Zinnoxyd oder Zinn-Instead of starting from already formed formic acid tin, one can also proceed in the same way process that formic acid (vapor) is poured over moderately heated tin oxide or tin
5 oxydul leitet, wobei vorübergehend ameisensaures Zinn gebildet wird, das sich dann gleich weiter zersetzt.5 oxydul conducts, whereby formic acid tin is temporarily formed, which is then immediately further decomposed.
Der Ameisensäuremethyläther kann entweder als solcher Benutzung rinden oder inThe formic acid methyl ether can either be used as such or in
ίο bekannter Weise in Methylalkohol und Ameisensäure gespalten werden. Mit Rücksicht auf die aus der Patentschrift 86419 bekannte technische Darstellung von Ameisensäure aus Kohlenoxyd ermöglicht das vorliegende Verfahren aus Kohlenoxyd, als Ausgangsstoff, Ameisensäure, Formaldehyd und Methylalkohol technisch herzustellen.ίο are known to be split into methyl alcohol and formic acid. With consideration on the technical representation of formic acid known from patent specification 86419 from carbon oxide enables the present process from carbon oxide, as a starting material, Manufacture of formic acid, formaldehyde and methyl alcohol industrially.
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE183856C true DE183856C (en) |
Family
ID=447838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT183856D Active DE183856C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE183856C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014130962A1 (en) * | 2013-02-24 | 2014-08-28 | Dioxide Materials, Inc. | Carbon dioxide conversion to fuels and chemicals |
| US8956990B2 (en) | 2010-03-26 | 2015-02-17 | Dioxide Materials, Inc. | Catalyst mixtures |
| US9012345B2 (en) | 2010-03-26 | 2015-04-21 | Dioxide Materials, Inc. | Electrocatalysts for carbon dioxide conversion |
| US9181625B2 (en) | 2010-03-26 | 2015-11-10 | Dioxide Materials, Inc. | Devices and processes for carbon dioxide conversion into useful fuels and chemicals |
| US9566574B2 (en) | 2010-07-04 | 2017-02-14 | Dioxide Materials, Inc. | Catalyst mixtures |
| US9790161B2 (en) | 2010-03-26 | 2017-10-17 | Dioxide Materials, Inc | Process for the sustainable production of acrylic acid |
| US9815021B2 (en) | 2010-03-26 | 2017-11-14 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
| US9957624B2 (en) | 2010-03-26 | 2018-05-01 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US10023967B2 (en) | 2010-03-26 | 2018-07-17 | Dioxide Materials, Inc. | Electrochemical devices employing novel catalyst mixtures |
| US10173169B2 (en) | 2010-03-26 | 2019-01-08 | Dioxide Materials, Inc | Devices for electrocatalytic conversion of carbon dioxide |
| US10647652B2 (en) | 2013-02-24 | 2020-05-12 | Dioxide Materials, Inc. | Process for the sustainable production of acrylic acid |
| US10975480B2 (en) | 2015-02-03 | 2021-04-13 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
-
0
- DE DENDAT183856D patent/DE183856C/de active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9555367B2 (en) | 2010-03-26 | 2017-01-31 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
| US9790161B2 (en) | 2010-03-26 | 2017-10-17 | Dioxide Materials, Inc | Process for the sustainable production of acrylic acid |
| US9012345B2 (en) | 2010-03-26 | 2015-04-21 | Dioxide Materials, Inc. | Electrocatalysts for carbon dioxide conversion |
| US9181625B2 (en) | 2010-03-26 | 2015-11-10 | Dioxide Materials, Inc. | Devices and processes for carbon dioxide conversion into useful fuels and chemicals |
| US9193593B2 (en) | 2010-03-26 | 2015-11-24 | Dioxide Materials, Inc. | Hydrogenation of formic acid to formaldehyde |
| US9464359B2 (en) | 2010-03-26 | 2016-10-11 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US8956990B2 (en) | 2010-03-26 | 2015-02-17 | Dioxide Materials, Inc. | Catalyst mixtures |
| US10173169B2 (en) | 2010-03-26 | 2019-01-08 | Dioxide Materials, Inc | Devices for electrocatalytic conversion of carbon dioxide |
| US10023967B2 (en) | 2010-03-26 | 2018-07-17 | Dioxide Materials, Inc. | Electrochemical devices employing novel catalyst mixtures |
| US9815021B2 (en) | 2010-03-26 | 2017-11-14 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
| US9957624B2 (en) | 2010-03-26 | 2018-05-01 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US9566574B2 (en) | 2010-07-04 | 2017-02-14 | Dioxide Materials, Inc. | Catalyst mixtures |
| WO2014130962A1 (en) * | 2013-02-24 | 2014-08-28 | Dioxide Materials, Inc. | Carbon dioxide conversion to fuels and chemicals |
| US10647652B2 (en) | 2013-02-24 | 2020-05-12 | Dioxide Materials, Inc. | Process for the sustainable production of acrylic acid |
| US10975480B2 (en) | 2015-02-03 | 2021-04-13 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
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