WO2017001874A1 - Method for the economic production of drinking water, especially deuterium depleted drinking water used in human and veterinary medicine - Google Patents

Method for the economic production of drinking water, especially deuterium depleted drinking water used in human and veterinary medicine Download PDF

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Publication number
WO2017001874A1
WO2017001874A1 PCT/HU2016/000042 HU2016000042W WO2017001874A1 WO 2017001874 A1 WO2017001874 A1 WO 2017001874A1 HU 2016000042 W HU2016000042 W HU 2016000042W WO 2017001874 A1 WO2017001874 A1 WO 2017001874A1
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Prior art keywords
deuterium
water
ppm
drinking water
content
Prior art date
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PCT/HU2016/000042
Other languages
French (fr)
Inventor
Elemér Antal ERDŐS
Katalin ERDŐSNÉ KUDRON
István KUDRON
Original Assignee
Erdős Elemér Antal
Erdősné Kudron Katalin
Kudron István
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Application filed by Erdős Elemér Antal, Erdősné Kudron Katalin, Kudron István filed Critical Erdős Elemér Antal
Publication of WO2017001874A1 publication Critical patent/WO2017001874A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/005—Systems or processes based on supernatural or anthroposophic principles, cosmic or terrestrial radiation, geomancy or rhabdomancy
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B5/00—Water
    • C01B5/02—Heavy water; Preparation by chemical reaction of hydrogen isotopes or their compounds, e.g. 4ND3 + 7O2 ---> 4NO2 + 6D2O, 2D2 + O2 ---> 2D2O
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
    • A61K35/02—Medicinal preparations containing materials or reaction products thereof with undetermined constitution from inanimate materials
    • A61K35/08—Mineral waters; Sea water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/026—Treating water for medical or cosmetic purposes

Definitions

  • the subject of the invention relates to a method for the economic production of deuterium-depleted drinking water (Deuterium Depleted Water, DDW), especially for the prevention of tumorous diseases, the alleviation of their symptoms and for therapeutic treatment.
  • DDW Deuterium Depleted Water
  • deuterium-depleted water In the field of medicine it is a well known and proven fact that significant results can be achieved with the use of deuterium-depleted water primarily in the early phase of tumorous diseases to prevent their spreading, in the slowing down of aging, and in many other fields of medicine as well. Apart from this, deuterium-depleted water may be a component in very many pharmaceutical preparations as it supplements the therapeutic effect of the basic active substance. In many cases it is only the high price of DDW that prevents it being used in more fields. Therefore, it is expected that there will be an increased demand for this water in the near future.
  • rock salt is decomposed by electrolysis on a mercury cathode in the process according to patent specification no HU217418.
  • An amalgam is formed from the metal sodium created.
  • the sodium- mercury amalgam becomes NaOH, and hydrogen is then made from this.
  • the hydrogen is purified, burned and condensed for the purpose of producing deuterium- depleted water.
  • this latter is subjected to rectification.
  • the operation is effective as it results in a D/H ratio of 50-60 ppm, however, its disadvantage is the high number of steps, the danger involved with the handling of hydrogen, and the low yield, in other words the significant costs due to these aspects.
  • the aim of the invention is the production of deuterium-depleted water in a way that is more economical than ever before, starting from water obtained easily and in large quantities as a combustion product of fossil hydrocarbons.
  • An important requirement and task at the same time is that an actual significant amount of the material should be available, which is produced at a cost that does not significantly increase the price of pharmaceutical preparations. Also, as the price of this product is reduced, its area of application increases. The reason for this is that the material obtained is not only useful on its own, but it can also be used as a solvent or reaction medium for other pharmaceutical preparations, and as an ingredient in foodstuff products, cosmetics, etc.
  • the initiator of the idea behind the invention was the publication by Robert C. Burruss and Christopher D. Laughrey entitled: "Covariation of carbon and hydrogen isotopic compositions in natural gas: separating biogenic, thermogenic, and abiotic (inorganic CO 2 reduction) sources", which was issued as a publication of the United States Geological Survey.
  • the publication is a comprehensive study of mineral hydrocarbons. It includes a study on the isotope composition distribution of the natural gases created in various ways according to their way of creation. However, it contains no information on the deuterium - hydrogen isotope ratio in the combustion water of methane.
  • the set aim may be solved with the collection and purification of the water created as the combustion product of fossil fuels, and with known distillation processes.
  • the water created as a combustion product is clean, sterile and its salt content is negligible. It is also a part of the recognition that large quantities of this water may be obtained simply and cheaply in numerous cases when other sources of water are limited or more expensive.
  • the method according to the invention for the economical production of deuterium depleted drinking water - DDW - used in human and veterinary medicine is based on that hydrocarbons of mineral origin are oxidised, the water created as a product of this is condensed, and in this way water with an average deuterium content of 122- 126 ppm is produced, which is lower than the natural deuterium content of 155 ppm, then preferably it is subjected to fractional distillation for the purpose of further deuterium depletion.
  • a further feature of the procedure according to the invention is that it is carried out directly or with a catalyst by burning the product of mineral origin, such as oil, oil derivatives or natural gas with the oxygen from the air or by reacting it with oxidising agents, during which the water vapour containing 122- 126 ppm deuterium is condensed from the combustion products using a cooling system, the water created is collected then preferably subjected to rectification for the purpose of further deuterium depletion.
  • a catalyst by burning the product of mineral origin, such as oil, oil derivatives or natural gas with the oxygen from the air or by reacting it with oxidising agents, during which the water vapour containing 122- 126 ppm deuterium is condensed from the combustion products using a cooling system, the water created is collected then preferably subjected to rectification for the purpose of further deuterium depletion.
  • the heat released during the burning of the mineral oil or gas is used for providing energy to the distillation equipment.
  • Making it suitable for human consumption is achieved by adding at least 1 g/1 of sodium hydrogen carbonate (NaHCOa) to the water with reduced deuterium content, then filtering it.
  • NaHCOa sodium hydrogen carbonate
  • the deuterium depleted water is passed through a bed consisting of crushed dolomite or limestone with a maximum grain size of 5 mm.
  • NaHCOa sodium hydrogen carbonate
  • the pH 3 value is neutralised to pH 7.
  • Other ions required for human consumption are also added as required.
  • the main advantage of the method according to the invention is that the basic raw materials consist of fossil hydrocarbons, mainly natural gas, the deuterium content of which among their hydrogen atoms is lower than what is usual from the outset. What is more, today in the developed world it is available almost everywhere in practically unlimited amounts. It is also favourable that the further reduction of the lower deuterium content requires fewer distillation steps. In this way the method is simpler and as a consequence of the factors mentioned until now, it is significantly more economical than any of the known procedures.
  • Example 1 The method is illustrated with the following examples without limiting the scope of protection to these examples alone.
  • Example 1 The method is illustrated with the following examples without limiting the scope of protection to these examples alone.
  • the calorific value of the natural gas was 35 MJ/m 3 .
  • the water from the combustion products was separated in a cooling system. It was found that the deuterium content of the separated water was 122 ppm.
  • a laboratory rectification device was filled with 6*6* 1.5 mm Raschig rings.
  • the device had a base with holes, and its glass column had a diameter of 50 mm and a height of 600 mm. Its outer surface was covered with textile heat insulation.
  • the column was placed on a 1.5 litre glass flask and an inclined water cooler was fitted at its top. 1 litre of deuterium depleted water, 125 ppm, prepared previously was filled into the flask and was then heated with an electric heater.
  • the boiling of the deuterium depleted water was stabilised by placing a number of Raschig rings into the flask. As a result of the boiling the water vapour produced gradually filled the rectification column. When the water appeared at the upper part of the column, the boiling was regulated so that we could take samples from the drips from the cooler coming at 1 / second. After a 50-cm 3 sample had been collected - representing 1 /20 separation - a spectrometer was used to measure the deuterium content, and was proven to be 121 ppm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The subject of the invention relates to a method for the economical production of deuterium depleted water - DDW. The invention's distinctive feature is that hydrocarbons of mineral origin are oxidised, the water created as a product of this is condensed, and in this way water with an average deuterium content lower than the natural deuterium content of 122- 126 ppm is produced, which is lower than the natural deuterium content of 155 ppm, then preferably it is subjected to fractional distillation for the purpose of further deuterium depletion.

Description

Method for the economic production of drinking water, especially deuterium depleted drinking water used in human and veterinary medicine
The subject of the invention relates to a method for the economic production of deuterium-depleted drinking water (Deuterium Depleted Water, DDW), especially for the prevention of tumorous diseases, the alleviation of their symptoms and for therapeutic treatment.
In the field of medicine it is a well known and proven fact that significant results can be achieved with the use of deuterium-depleted water primarily in the early phase of tumorous diseases to prevent their spreading, in the slowing down of aging, and in many other fields of medicine as well. Apart from this, deuterium-depleted water may be a component in very many pharmaceutical preparations as it supplements the therapeutic effect of the basic active substance. In many cases it is only the high price of DDW that prevents it being used in more fields. Therefore, it is expected that there will be an increased demand for this water in the near future.
Numerous successful solutions have been developed in the specialist field relating to the production of this product. Distillation and rectification methods have become widespread in order to achieve depleted deuterium content. A difficulty is presented by the low separation factor in H2O, HDO, D2O systems, due to the hardly 1 °C difference in boiling point (at 1 bar of pressure). These columns operate with a large number of plates; due to this column systems are costly. This may be read in patent specifications registration numbers RU2295493 and HU 208084. According to the procedure presented in Chinese patent specification number 101481088, DDW is produced through the fractional distillation of the initial water in a plastic composite column. This is also a complex procedure demanding a large plate number. Another widespread method is electrochemical water decomposition producing and burning hydrogen. The difference in the separation voltages of protium and deuterium is the basis of protium enrichment. This may be read in patent specification registration number RU 101648.
Among the solutions known previously, rock salt is decomposed by electrolysis on a mercury cathode in the process according to patent specification no HU217418. An amalgam is formed from the metal sodium created. On coming into contact with water the sodium- mercury amalgam becomes NaOH, and hydrogen is then made from this. The hydrogen is purified, burned and condensed for the purpose of producing deuterium- depleted water. In order to further reduce the deuterium content this latter is subjected to rectification. The operation is effective as it results in a D/H ratio of 50-60 ppm, however, its disadvantage is the high number of steps, the danger involved with the handling of hydrogen, and the low yield, in other words the significant costs due to these aspects.
The aim of the invention is the production of deuterium-depleted water in a way that is more economical than ever before, starting from water obtained easily and in large quantities as a combustion product of fossil hydrocarbons. An important requirement and task at the same time is that an actual significant amount of the material should be available, which is produced at a cost that does not significantly increase the price of pharmaceutical preparations. Also, as the price of this product is reduced, its area of application increases. The reason for this is that the material obtained is not only useful on its own, but it can also be used as a solvent or reaction medium for other pharmaceutical preparations, and as an ingredient in foodstuff products, cosmetics, etc.
The initiator of the idea behind the invention was the publication by Robert C. Burruss and Christopher D. Laughrey entitled: "Covariation of carbon and hydrogen isotopic compositions in natural gas: separating biogenic, thermogenic, and abiotic (inorganic CO2 reduction) sources", which was issued as a publication of the United States Geological Survey. The publication is a comprehensive study of mineral hydrocarbons. It includes a study on the isotope composition distribution of the natural gases created in various ways according to their way of creation. However, it contains no information on the deuterium - hydrogen isotope ratio in the combustion water of methane.
The basis of the idea behind the invention was the recognition that a study should be performed to determine what is obtained from samples of the combustion products of various burnt natural gases. After taking the samples, the combustion products were examined using mass spectrometry, compared and the surprising result was obtained, which was in no way obvious, that the 2H isotope, in other words deuterium, occurs in a smaller proportion among the hydrogen atoms bound in fossil hydrocarbons.
In possession of this recognition the set aim may be solved with the collection and purification of the water created as the combustion product of fossil fuels, and with known distillation processes. The water created as a combustion product is clean, sterile and its salt content is negligible. It is also a part of the recognition that large quantities of this water may be obtained simply and cheaply in numerous cases when other sources of water are limited or more expensive.
In accordance with the set aim the method according to the invention for the economical production of deuterium depleted drinking water - DDW - used in human and veterinary medicine is based on that hydrocarbons of mineral origin are oxidised, the water created as a product of this is condensed, and in this way water with an average deuterium content of 122- 126 ppm is produced, which is lower than the natural deuterium content of 155 ppm, then preferably it is subjected to fractional distillation for the purpose of further deuterium depletion.
A further feature of the procedure according to the invention is that it is carried out directly or with a catalyst by burning the product of mineral origin, such as oil, oil derivatives or natural gas with the oxygen from the air or by reacting it with oxidising agents, during which the water vapour containing 122- 126 ppm deuterium is condensed from the combustion products using a cooling system, the water created is collected then preferably subjected to rectification for the purpose of further deuterium depletion.
During a preferable realisation of the method according to the invention, the heat released during the burning of the mineral oil or gas is used for providing energy to the distillation equipment.
Making it suitable for human consumption is achieved by adding at least 1 g/1 of sodium hydrogen carbonate (NaHCOa) to the water with reduced deuterium content, then filtering it. In another case it is preferable if the deuterium depleted water is passed through a bed consisting of crushed dolomite or limestone with a maximum grain size of 5 mm. With the above measures the acidity of the water originating from the burning of hydrocarbons is terminated with sodium hydrogen carbonate (NaHCOa) treatment or, in another case, by passing the water through a base (alkaline) bed of limestone or dolomite stone, in other words the pH 3 value is neutralised to pH 7. Other ions required for human consumption are also added as required.
The main advantage of the method according to the invention is that the basic raw materials consist of fossil hydrocarbons, mainly natural gas, the deuterium content of which among their hydrogen atoms is lower than what is usual from the outset. What is more, today in the developed world it is available almost everywhere in practically unlimited amounts. It is also favourable that the further reduction of the lower deuterium content requires fewer distillation steps. In this way the method is simpler and as a consequence of the factors mentioned until now, it is significantly more economical than any of the known procedures.
The method is illustrated with the following examples without limiting the scope of protection to these examples alone. Example 1
Several litres of cold water were heated over a gas flame in a stainless steel pan on a household gas cooker. A sample was then taken from the drops of condensate on the outer side of the tilted pan. The sample was tested and its deuterium content determined by mass spectrometry was 125 ppm.
Example 2
Natural gas was burnt with air in a household gas boiler (CH4 + 2Ο2 = CO2 + 2H2O) . The calorific value of the natural gas was 35 MJ/m3. The water from the combustion products was separated in a cooling system. It was found that the deuterium content of the separated water was 122 ppm.
Example 3
All of the steps of example 2 were carried out, then, in order to make the water suitable for human consumption, 1 g/1 of sodium hydrogen carbonate (NaHCOa) was added to the water, which was then filtered.
Example 4
Once again, all the steps of example 2 were performed, then in order to make the water suitable for human consumption the water was passed through a limestone bed with an average grain size of 5 mm, then the water was filtered. In all cases the water was potable.
Example 5
A laboratory rectification device was filled with 6*6* 1.5 mm Raschig rings. The device had a base with holes, and its glass column had a diameter of 50 mm and a height of 600 mm. Its outer surface was covered with textile heat insulation. The column was placed on a 1.5 litre glass flask and an inclined water cooler was fitted at its top. 1 litre of deuterium depleted water, 125 ppm, prepared previously was filled into the flask and was then heated with an electric heater.
The boiling of the deuterium depleted water was stabilised by placing a number of Raschig rings into the flask. As a result of the boiling the water vapour produced gradually filled the rectification column. When the water appeared at the upper part of the column, the boiling was regulated so that we could take samples from the drips from the cooler coming at 1 / second. After a 50-cm3 sample had been collected - representing 1 /20 separation - a spectrometer was used to measure the deuterium content, and was proven to be 121 ppm.
The mass spectrometry isotope composition tests performed by the Geochemical Institute of the Hungarian Academy of Sciences confirmed our expectations. Gas obtained from households in several locations in Hungary was burnt. The deuterium content of the water coming from the combustion products fluctuated between 122 and 126 ppm.
The significance of the method forming the basis of the invention lies in that a new raw material is proposed which is available almost everywhere, furthermore, the method contains fewer steps than previously known methods. Therefore it is preferable to them, both from the technical and economic points of view.

Claims

Claims
1. Method for the economical production of deuterium depleted water - DDW, characterised by that hydrocarbons of mineral origin are oxidised, the water created as a product of this is condensed, and in this way water with an average deuterium content lower than the natural deuterium content of 122- 126 ppm is produced, which is lower than the natural deuterium content of 155 ppm, then preferably it is subjected to fractional distillation for the purpose of further deuterium depletion.
2. Method according to claim 1 , characterised by that it is carried out directly or with a catalyst by burning the product of mineral origin, such as oil, oil derivatives or natural gas, with the oxygen from the air or by reacting it with oxidising agents, during which the water vapour containing 122- 126 ppm deuterium is condensed from the combustion products using a cooling system, the water created is collected then preferably subjected to rectification for the purpose of further deuterium depletion.
3. Method according to claim 2, characterised by that the heat released during the burning of the mineral oil or gas is used for providing energy to the distillation equipment.
4. Method according to claim 1 or 2, characterised by that before human consumption at least 1 g/1 of sodium hydrogen carbonate (NaHCOs) is added to the water with reduced deuterium content, then it is filtered.
5. Method according to claim 1 or 2, characterised by that that before human consumption the deuterium depleted water is passed through a base (alkaline) bed consisting of, for example, crushed dolomite or limestone with a maximum grain size of 5 mm.
PCT/HU2016/000042 2015-06-29 2016-06-27 Method for the economic production of drinking water, especially deuterium depleted drinking water used in human and veterinary medicine WO2017001874A1 (en)

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HUP1500301 2015-06-29
HU1500301A HU230921B1 (en) 2015-06-29 2015-06-29 A method for the economical production of a reduced deuterium containing water used in medicine

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019134014A1 (en) 2018-01-02 2019-07-11 Ambrosios Kambouris Isotopic compositions ii
WO2019174659A1 (en) 2018-03-15 2019-09-19 Karl Bau Gmbh Method and assembly for producing water having reduced deuterium content
RU2801453C2 (en) * 2018-01-02 2023-08-08 БОТЭНИКЕЛ УОТЕР ТЕКНОЛОДЖИС АйПи ЛТД Isotope compositions ii

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB754745A (en) * 1953-04-02 1956-08-15 Montedison Spa Improvements in and relating to methods and apparatus for producing pure boiler feedwater
GB1371269A (en) * 1971-03-26 1974-10-23 Erno Raumfahrttechnik Gmbh Process for the production of water
WO1996033129A1 (en) * 1995-04-20 1996-10-24 Kotai Laszlo A chemical procedure to produce water of reduced deuterium content
TW201041806A (en) * 2009-05-26 2010-12-01 Microbio Co Ltd Method for producing water of low heavy oxygen and deuterium content and distillation device thereof
US20150110708A1 (en) * 2013-10-23 2015-04-23 Air Products And Chemical Inc. Integrated Process for the Production of Hydrogen and Water

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB754745A (en) * 1953-04-02 1956-08-15 Montedison Spa Improvements in and relating to methods and apparatus for producing pure boiler feedwater
GB1371269A (en) * 1971-03-26 1974-10-23 Erno Raumfahrttechnik Gmbh Process for the production of water
WO1996033129A1 (en) * 1995-04-20 1996-10-24 Kotai Laszlo A chemical procedure to produce water of reduced deuterium content
TW201041806A (en) * 2009-05-26 2010-12-01 Microbio Co Ltd Method for producing water of low heavy oxygen and deuterium content and distillation device thereof
US20150110708A1 (en) * 2013-10-23 2015-04-23 Air Products And Chemical Inc. Integrated Process for the Production of Hydrogen and Water

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019134014A1 (en) 2018-01-02 2019-07-11 Ambrosios Kambouris Isotopic compositions ii
RU2801453C2 (en) * 2018-01-02 2023-08-08 БОТЭНИКЕЛ УОТЕР ТЕКНОЛОДЖИС АйПи ЛТД Isotope compositions ii
WO2019174659A1 (en) 2018-03-15 2019-09-19 Karl Bau Gmbh Method and assembly for producing water having reduced deuterium content

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HUP1500301A2 (en) 2017-01-30

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