DE4036787A1 - Safe, environmentally friendly destruction of explosives - pref. propellant powder, by hydrolytic cleavage followed by biological degradation in a clarifying plant - Google Patents
Safe, environmentally friendly destruction of explosives - pref. propellant powder, by hydrolytic cleavage followed by biological degradation in a clarifying plantInfo
- Publication number
- DE4036787A1 DE4036787A1 DE19904036787 DE4036787A DE4036787A1 DE 4036787 A1 DE4036787 A1 DE 4036787A1 DE 19904036787 DE19904036787 DE 19904036787 DE 4036787 A DE4036787 A DE 4036787A DE 4036787 A1 DE4036787 A1 DE 4036787A1
- Authority
- DE
- Germany
- Prior art keywords
- pref
- explosives
- safe
- hydrolytic cleavage
- environmentally friendly
- 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.)
- Granted
Links
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/02—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F42—AMMUNITION; BLASTING
- F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
- F42B33/00—Manufacture of ammunition; Dismantling of ammunition; Apparatus therefor
- F42B33/06—Dismantling fuzes, cartridges, projectiles, missiles, rockets or bombs
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/06—Explosives, propellants or pyrotechnics, e.g. rocket fuel or napalm
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Biomedical Technology (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Vernichtung von Explosivstoffen, ins besondere von Treibladungspulvern.The invention relates to a method for the destruction of explosives, ins special of propellant powders.
Im Rahmen der Abrüstung müssen sehr große Mengen Munition vernichtet werden. Der größte Teil besteht aus Explosivstoffen bzw. Treibladungspul vern.Very large amounts of ammunition must be destroyed as part of the disarmament will. The largest part consists of explosives or propellant charge neg.
Bekannt sind Vernichtungsverfahren durch Verbrennen, Ausbrennen, Aus glühen, Sprengen oder Verschießen. Alle diese Verfahren weisen aber er hebliche Nachteile auf:Annihilation processes by burning, burning out, out are known glowing, blowing up or shooting. But he shows all these procedures major disadvantages:
Durch lokale Ungleichgewichte, Hot Spots oder katalytische Einflüsse kann in manchen Fällen ungewollt aus dem Ab- oder Verbren nen eine Detonation werden, was die entsprechende Anlage beschädigen oder zerstören kann.Through local imbalances, hot spots or catalytic In some cases, influences can be unintentional from burning off or burning detonation can damage the system or can destroy.
Beim Abbrennen der Explosivstoffe wird das stoffliche Problem in aggressive Produktgase verlagert, die wiederum gereinigt werden müs sen, wobei dann wieder flüssige oder feste Abfälle entstehen, die ihrer seits zu entsorgen sind.When the explosives burn off, the material problem becomes shifted into aggressive product gases, which in turn have to be cleaned sen, whereupon liquid or solid waste is generated again, which is their are to be disposed of.
Aus den geschätzten 40 000 t Explosivstoffen des heutigen NVA-Bestandes werden beim Deflagrieren grob 40 Mio m3 sehr aggressiver Gase (vor allem NOx), wobei die Zusammensetzung der Gase je nach Verbrennungsparametern und Munitionsart erheblichen Schwan kungen unterworfen ist. Gasreinigungsanlagen, die darauf einstellbar sind, gibt es in der notwendigen Größenordnung nicht.During the deflagration, roughly 40 million m 3 of very aggressive gases (especially NO x ) are made from the estimated 40,000 t of explosives from today's NVA stock, whereby the composition of the gases is subject to considerable fluctuations depending on the combustion parameters and the type of ammunition. There are no gas cleaning systems that can be adjusted to the required size.
Aus diesen Gründen ist ein Vernichtungsverfahren wünschenswert, das ohne die beschriebenen Nachteile arbeitet.For these reasons, an annihilation process that does not require the disadvantages described works.
Aufgabe der Erfindung ist es, ein Vernichtungsverfahren für Explosivstoffe, speziell für Treibladungspulver vorzuschlagen, das sicher und umweltverträg lich ist und sich für große Mengen eignet.The object of the invention is to provide a method of destruction for explosives, propose specifically for propellant powder that is safe and environmentally friendly Lich and is suitable for large quantities.
Diese Aufgabe wird erfindungsgemäß gelöst durch die hydrolytische Spaltung der Treibladungspulver, die Neutralisierung der entstehenden Lösung und den anschließenden biologischen Abbau mit den Merkmalen des Hauptan spruches.According to the invention, this object is achieved by the hydrolytic cleavage the propellant powder, the neutralization of the resulting solution and the subsequent biodegradation with the characteristics of the main saying.
Ausführungen der Erfindung sind Gegenstände von Unteransprüchen.Embodiments of the invention are the subject of subclaims.
Die aus den Munitionen entfernten oder in die Säckchen abgefüllten Treibla dungspulver für Artilleriegeschosse bestehen aus unterschiedlichsten Kompo nenten. Die Hauptbestandteile sind jedoch:The driftwood removed from the ammunition or filled into the sacks Powder for artillery projectiles consists of a wide variety of compos nenten. The main components, however, are:
- - Nitrocellulose, - nitrocellulose,
- - Nitroguanidin,- nitroguanidine,
- - Nitroglycerin,- nitroglycerin,
- - Dinitroglycerin,- dinitroglycerin,
- - Di-, Triglykoldinitrat,- di-, triglycol dinitrate,
- - Nitrotoluole.- nitrotoluenes.
Bei den Verbindungen handelt es sich um Salpetersäureester von organi schen Verbindungen bzw. um Nitroverbindungen. Sogar die ebenfalls in ge ringen Mengen im Pulver enthaltenen Stabilisatoren wie Akardit oder Centralit bestehen aus organischen Grundstoffen (Harnstoffderivate). Diese Verbindun gen können hydrolytisch gespalten werden, wenn man die Pulver in alkali sche wäßrige Medien gibt. Durch Reaktion mit Laugen in wäßriger Lösung (z. B. Na OH, KOH oder Ca (OH)2) entsteht eventuell unter Hinzugabe eines Lösungsvermittlers aus Nitrocellulose z. B. im Wasser gelöstes Nitrat und reine Cellulose.The compounds are nitric acid esters of organic compounds or nitro compounds. Even the stabilizers such as acardite or centralite, which are also contained in small amounts in the powder, consist of organic raw materials (urea derivatives). These compounds can be hydrolytically cleaved if the powders are added to alkaline aqueous media. By reaction with alkalis in aqueous solution (e.g. Na OH, KOH or Ca (OH) 2 ), possibly with the addition of a solubilizer made of nitrocellulose z. B. nitrate dissolved in water and pure cellulose.
Summarische Grundreaktion der Nitrate (R-NO3) ist:The basic summary reaction of the nitrates (R-NO 3 ) is:
R-NO3+ OH⁻ R-OH + NO3⁻.R-NO 3 + OH⁻ R-OH + NO 3 ⁻.
Summarische Grundreaktion der Nitroverbindung (R-NO2) ist:The basic summary reaction of the nitro compound (R-NO 2 ) is:
R-NO2+ OH⁻ R-H + NO3⁻.R-NO 2 + OH⁻ RH + NO 3 ⁻.
Neben dem in wäßriger Lösung entstehenden Nitrat (NO3⁻) kann durch Ne benreaktionen auch Nitrit (NO2⁻) entstehen. In addition to the nitrate (NO 3 ⁻) formed in aqueous solution, nitrite (NO 2 ⁻) can also be formed by side reactions.
Bei der Reaktion der genannten Bestandteile der Treibladungspulver entste hen im Wasser gelöstes Nitrat und Nitrit sowie die zugehörigen organischen Verbindungen (bzw. weitere Hydrolyseprodukte dieser Verbindungen):The propellant powder is formed during the reaction of the components mentioned hen dissolved in water nitrate and nitrite and the associated organic Compounds (or other hydrolysis products of these compounds):
- - Cellulose,- cellulose,
- - Guanidin,- guanidine,
- - Glycerin,- glycerin,
- - Glykol,- glycol,
- - Toluol.- toluene.
Die schwer löslichen Bestandteile wie z. B. Cellulose bilden dabei einen schlammigen Bodensatz, der Rest geht in Lösung.The difficultly soluble components such. B. cellulose form a muddy sediment, the rest goes into solution.
Alle diese Reaktionsprodukte des ersten Schrittes sind biologisch abbaubar. Nach Senken des pH-Werts oder einer Neutralisierung mit einer Säure auf z. B. pH 7 könnte daher die gesamte Lösung in eine entsprechend ausgelegte biologische Kläranlage eingeleitet werden.All of these reaction products from the first step are biodegradable. After lowering the pH or neutralizing with an acid e.g. B. pH 7 could therefore the entire solution in an appropriately designed biological treatment plant.
Die Klärung erfolgt in Wasserbecken, deren Hintereinanderschaltung und Prozeßführung dem spezifischen Abwasser angepaßt ist. Ein wichtiger Hauptbestandteil ist eine Denitrifikationsstufe, in der in einem anaeroben Prozeß Bakterien wie z. B. Pseudomonas, Micrococcus oder Denitrobacillus die organischen Bestandteile wie Cellulose, Guanidin usw. in ihre Bausteine zerlegen und das im Wasser gelöste Nitrat als Sauerstofflieferant benutzen. Dabei werden sowohl die organischen Bestandteile als auch das Nitrat aus dem Wasser entfernt, wobei unter Bildung von gasförmigem Stickstoff sich die entsprechende Biomasse bildet. Nach dem Absetzbecken kann das geklärte Wasser in einen Vorfluter abgeleitet und der Schlamm in der Weise weiterver arbeitet werden, wie es in eingeführten Kläranlagen mit biologischer Reini gungsstufe üblich ist, z. B. als Dünger in der Landwirtschaft oder zur Energie gewinnung über die Methangasbildung in einem Faulturm. Die Schlammver wendung erscheint unproblematischer als bei kommunalen Kläranlagen, da eine Kontamination mit Schwermetallen kaum zu befürchten ist.The clarification takes place in water basins, their connection in series and Process control is adapted to the specific wastewater. An important The main component is a denitrification stage, in which anaerobic Process bacteria such as B. Pseudomonas, Micrococcus or Denitrobacillus the organic components such as cellulose, guanidine etc. in their building blocks disassemble and use the nitrate dissolved in the water as an oxygen supplier. This removes both the organic components and the nitrate removed from the water, with the formation of gaseous nitrogen corresponding biomass forms. After the sedimentation tank that can be clarified Water is drained into a receiving water and the sludge is further processed be operated as it is in established sewage plants with biological purification is usual, z. B. as fertilizer in agriculture or for energy extraction via methane gas formation in a digester. The Schlammver application seems less problematic than with municipal wastewater treatment plants, because contamination with heavy metals is hardly to be feared.
Im Vergleich zu den herkömmlichen Verfahren (Verbrennen) ist das erfin dungsgemäße Verfahren einfacher und ungefährlicher. Da die Vernichtung in wäßriger Lösung abläuft, bestehen keine Sicherheitsprobleme durch unge wollte Detonationen. Die Reststoffe (Klärschlamm bzw. Dünger) sind weiter verwendbar. Die Umwelt wird nicht belastet. Da aus 40 000 t Treibladungspul ver je nach Konzentration der Lösung ca. 100 000-300 000 m3 Abwasser, die in der Kläranlage zu behandeln sind, werden (im Vergleich zu 40 Mio m3 aggressives Gas bei Verbrennung) ist auch die Munitionsmenge nicht mehr das hervorragende Problem. Denn biologische Kläranlagen mit Millionen m3 Durchsatz pro Jahr sind Standard.In comparison to the conventional methods (combustion), the method according to the invention is simpler and less dangerous. Since the destruction takes place in aqueous solution, there are no safety problems due to unwanted detonations. The residues (sewage sludge or fertilizer) can still be used. The environment is not polluted. Since 40,000 t of propellant powder, depending on the concentration of the solution, turns out to be about 100,000-300,000 m 3 of wastewater to be treated in the sewage treatment plant (compared to 40 million m 3 of aggressive gas when burned), the amount of ammunition is also not more the excellent problem. Because biological wastewater treatment plants with a throughput of millions m 3 per year are standard.
Der oder die ersten Schritte (hydrolytische Spaltung, Neutralisierung) können vorteilhaft in verfahrbaren Behältern (Containern, Tanks) durchgeführt wer den, die dann zu den vorgesehenen Kläranlagen gefahren werden.The first step or steps (hydrolytic cleavage, neutralization) can advantageously carried out in mobile containers (containers, tanks) those who are then driven to the designated sewage treatment plants.
Claims (5)
- a) hydrolytische Spaltung und
- b) anschließendem Abbau in einer biologischen Kläranlage.
- a) hydrolytic cleavage and
- b) subsequent degradation in a biological sewage treatment plant.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19904036787 DE4036787A1 (en) | 1990-11-17 | 1990-11-17 | Safe, environmentally friendly destruction of explosives - pref. propellant powder, by hydrolytic cleavage followed by biological degradation in a clarifying plant |
CH316691A CH682459A5 (en) | 1990-11-17 | 1991-10-30 | A method for destroying explosives. |
CS913473A CS347391A3 (en) | 1990-11-17 | 1991-11-15 | Process of explosives decomposition |
PL29241791A PL292417A1 (en) | 1990-11-17 | 1991-11-15 | Method of annihilating explosives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19904036787 DE4036787A1 (en) | 1990-11-17 | 1990-11-17 | Safe, environmentally friendly destruction of explosives - pref. propellant powder, by hydrolytic cleavage followed by biological degradation in a clarifying plant |
Publications (2)
Publication Number | Publication Date |
---|---|
DE4036787A1 true DE4036787A1 (en) | 1992-05-21 |
DE4036787C2 DE4036787C2 (en) | 1993-06-17 |
Family
ID=6418522
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19904036787 Granted DE4036787A1 (en) | 1990-11-17 | 1990-11-17 | Safe, environmentally friendly destruction of explosives - pref. propellant powder, by hydrolytic cleavage followed by biological degradation in a clarifying plant |
Country Status (4)
Country | Link |
---|---|
CH (1) | CH682459A5 (en) |
CS (1) | CS347391A3 (en) |
DE (1) | DE4036787A1 (en) |
PL (1) | PL292417A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5763736A (en) * | 1997-02-13 | 1998-06-09 | Oerlikon Contraves Pyrotec Ag | Method for the disposal of explosive material |
WO1998053105A1 (en) * | 1997-05-21 | 1998-11-26 | Lockheed Martin Idaho Technologies Company | Method for the decontamination of soil containing solid organic explosives therein |
WO1998053884A1 (en) * | 1997-05-27 | 1998-12-03 | Vericore Limited | Degradation of hazardous chemicals |
WO1999013950A1 (en) * | 1997-09-18 | 1999-03-25 | Alliedsignal Inc. | Demilitarization of chemical munitions |
ES2131478A1 (en) * | 1997-10-27 | 1999-07-16 | Pastor Alicia Guijarro | Method for converting explosive substances into fertilizers by means of a process using KOH (potassium hydroxide) as hydrolysis agent |
WO2000015306A1 (en) * | 1998-09-14 | 2000-03-23 | Alliedsignal Inc. | Demilitarization of chemical munitions |
WO2001010504A2 (en) * | 1999-08-06 | 2001-02-15 | Honeywell | Treatment of chemical hydrolysates |
WO2001062346A2 (en) * | 2000-02-23 | 2001-08-30 | Uxb International, Inc. | Destruction of energetic materials |
US6543535B2 (en) | 2000-03-15 | 2003-04-08 | Exxonmobil Upstream Research Company | Process for stimulating microbial activity in a hydrocarbon-bearing, subterranean formation |
ES2259575A1 (en) * | 2006-03-31 | 2006-10-01 | Arturo Diaz De Barrionuevo | Integral recuperation of high energy content products comprises disarming of projectiles for explosives alkaline hydrolysis and regeneration of the inert matter |
US7845403B2 (en) | 2005-05-03 | 2010-12-07 | Luca Technologies, Inc. | Biogenic fuel gas generation in geologic hydrocarbon deposits |
US8715978B2 (en) | 2004-05-12 | 2014-05-06 | Transworld Technologies Inc. | Generation of hydrogen from hydrocarbon bearing materials |
US9004162B2 (en) | 2012-03-23 | 2015-04-14 | Transworld Technologies Inc. | Methods of stimulating acetoclastic methanogenesis in subterranean deposits of carbonaceous material |
US9458375B2 (en) | 2006-04-05 | 2016-10-04 | Transworld Technologies Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EA008624B1 (en) | 2003-08-15 | 2007-06-29 | Перма-Фикс Инвайроментал Сервисез, Инк. | Treatment of chemical agent hydrolysates |
US8492607B2 (en) | 2003-08-15 | 2013-07-23 | Perma-Fix Environmental Services, Inc. | Treatment of chemical agent hydrolysates |
US7416879B2 (en) | 2006-01-11 | 2008-08-26 | Luca Technologies, Inc. | Thermacetogenium phaeum consortium for the production of materials with enhanced hydrogen content |
US7977282B2 (en) | 2006-04-05 | 2011-07-12 | Luca Technologies, Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
US8479813B2 (en) | 2009-12-16 | 2013-07-09 | Luca Technologies, Inc. | Biogenic fuel gas generation in geologic hydrocarbon deposits |
-
1990
- 1990-11-17 DE DE19904036787 patent/DE4036787A1/en active Granted
-
1991
- 1991-10-30 CH CH316691A patent/CH682459A5/en not_active IP Right Cessation
- 1991-11-15 CS CS913473A patent/CS347391A3/en unknown
- 1991-11-15 PL PL29241791A patent/PL292417A1/en unknown
Non-Patent Citations (4)
Title |
---|
"Lehrbuch der organischen Chemie" von W. Langenbeck, 1952, S. 46/47 * |
CA 107(26):241949z (1987) * |
SCHLEGEL, Hans G.: Allgemeine Mikrobiologie, 4. Aufl., 1976, S. 268-271 und 336-338 * |
ULLMANN: Encyklopädie der technischen Chemie, 3. Aufl., Bd. 12, 1960, S. 791 * |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5763736A (en) * | 1997-02-13 | 1998-06-09 | Oerlikon Contraves Pyrotec Ag | Method for the disposal of explosive material |
EP0858816A1 (en) * | 1997-02-13 | 1998-08-19 | Oerlikon-Contraves Pyrotec AG | Process for treating explosives |
WO1998053105A1 (en) * | 1997-05-21 | 1998-11-26 | Lockheed Martin Idaho Technologies Company | Method for the decontamination of soil containing solid organic explosives therein |
US6051420A (en) * | 1997-05-21 | 2000-04-18 | Bechtel Bwxt Idaho, Llc | Method for the decontamination of soil containing solid organic explosives therein |
WO1998053884A1 (en) * | 1997-05-27 | 1998-12-03 | Vericore Limited | Degradation of hazardous chemicals |
WO1999013950A1 (en) * | 1997-09-18 | 1999-03-25 | Alliedsignal Inc. | Demilitarization of chemical munitions |
CN1121886C (en) * | 1997-09-18 | 2003-09-24 | 联合讯号公司 | Demilitarization of chemical munitions |
ES2131478A1 (en) * | 1997-10-27 | 1999-07-16 | Pastor Alicia Guijarro | Method for converting explosive substances into fertilizers by means of a process using KOH (potassium hydroxide) as hydrolysis agent |
WO2000015306A1 (en) * | 1998-09-14 | 2000-03-23 | Alliedsignal Inc. | Demilitarization of chemical munitions |
WO2001010504A2 (en) * | 1999-08-06 | 2001-02-15 | Honeywell | Treatment of chemical hydrolysates |
GB2370036A (en) * | 1999-08-09 | 2002-06-19 | Honeywell Inc | Treatment of chemical hydrolysates |
WO2001010504A3 (en) * | 1999-08-09 | 2001-09-13 | Honeywell | Treatment of chemical hydrolysates |
GB2370036B (en) * | 1999-08-09 | 2003-07-02 | Honeywell Int Inc | Treatment of chemical munitions agent hydrolysates |
US6603050B2 (en) | 2000-02-23 | 2003-08-05 | Uxb International, Inc. | Destruction of energetic materials |
WO2001062346A2 (en) * | 2000-02-23 | 2001-08-30 | Uxb International, Inc. | Destruction of energetic materials |
WO2001062346A3 (en) * | 2000-02-23 | 2002-04-18 | Uxb International Inc | Destruction of energetic materials |
US6543535B2 (en) | 2000-03-15 | 2003-04-08 | Exxonmobil Upstream Research Company | Process for stimulating microbial activity in a hydrocarbon-bearing, subterranean formation |
US8715978B2 (en) | 2004-05-12 | 2014-05-06 | Transworld Technologies Inc. | Generation of hydrogen from hydrocarbon bearing materials |
US9057082B2 (en) | 2004-05-12 | 2015-06-16 | Transworld Technologies Inc. | Generation of methane from hydrocarbon bearing materials |
US8794315B2 (en) | 2005-05-03 | 2014-08-05 | Transworld Technologies Inc. | Biogenic fuel gas generation in geologic hydrocarbon deposits |
US7845403B2 (en) | 2005-05-03 | 2010-12-07 | Luca Technologies, Inc. | Biogenic fuel gas generation in geologic hydrocarbon deposits |
US9434872B2 (en) | 2005-05-03 | 2016-09-06 | Transworld Technologies Inc. | Biogenic fuel gas generation in geologic hydrocarbon deposits |
ES2259575A1 (en) * | 2006-03-31 | 2006-10-01 | Arturo Diaz De Barrionuevo | Integral recuperation of high energy content products comprises disarming of projectiles for explosives alkaline hydrolysis and regeneration of the inert matter |
US9458375B2 (en) | 2006-04-05 | 2016-10-04 | Transworld Technologies Inc. | Chemical amendments for the stimulation of biogenic gas generation in deposits of carbonaceous material |
US9004162B2 (en) | 2012-03-23 | 2015-04-14 | Transworld Technologies Inc. | Methods of stimulating acetoclastic methanogenesis in subterranean deposits of carbonaceous material |
Also Published As
Publication number | Publication date |
---|---|
CH682459A5 (en) | 1993-09-30 |
CS347391A3 (en) | 1992-08-12 |
PL292417A1 (en) | 1992-08-24 |
DE4036787C2 (en) | 1993-06-17 |
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8331 | Complete revocation |