• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A deoxygenation process includes the steps of adding hydrazine to a liquid containing dissolved oxygen, passing the liquid through a bed of activated carbon to catalyze a reaction between the dissolved oxygen and hydrazine whereby carbon contaminants are added to the liquid, and removing the contaminants. In another embodiment, unreacted hydrazine that remains in the liquid following the catalysis is removed by passing the liquid through an ion exchange resin. In still another embodiment, an activated carbon-catalyzed deoxygenation process employing hydrazine is practiced on a mobile platform and the process further includes the steps of transporting the apparatus to a regenerating station for regeneration. The invention also includes apparatus for carrying out the process.
    公开号:SU1757455A3
    申请号:SU853947156
    申请日:1985-08-15
    公开日:1992-08-23
    发明作者:С.Дикерсон Ричард；С.Миллер Уильям
    申请人:Эколокем, Инк. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a method for removing dissolved oxygen from liquids using hydrazine and coal as a catalyst.
    Methods for removing oxygen dissolved in liquids from liquids have a very wide range of applications. In a number of industries, including the manufacture of beverages, electronics, space technology, deep drilling and energy production, water is used in large quantities, and the presence of dissolved oxygen in too large quantities can cause undesirable consequences, including deterioration of product quality and corrosion. power equipment, especially in closed circulation systems.
    In the prior art oxygen removal method, hydrazine is used as a highly effective reducing agent to solve the problems of corrosion and others associated with the use of oxygenated water.
    In this reaction, hydrazine with dissolved oxygen is catalyzed by passing water through an activated carbon layer.
    The lack of a method for the catalytic removal of oxygen is due to the penetration of contaminants into the oxygen-free liquid, for example, unreacted
    XI ate VI
    -fck ate
    | SL

    CJ
    hydrazine, coal and other contaminants.
    In cases where a certain amount of unreacted hydrazine in the circulating water is desirable to prevent corrosion of energy equipment, the known method has remained unacceptable because it does not allow to regulate the amount of unreacted hydrazine and ensure the presence of its optimal amount in the circulating water. So, when choosing the optimal amount of reactive hydrazine in the oxygen removal stage, the amount of residual hydrazine can be either greater or less than the optimal one in the circulation stage. With a low level of hydrazine at the circulation stage, it loses its anticorrosive efficiency, and at too high a level it can cause an unacceptable increase in the pH value and electrical conductivity of the circulating water.
    The purpose of the invention is to provide the possibility of using deoxygenated water in a closed circulation system by flexibly controlling the amount of unreacted hydrazine in water, reducing the content of carbon impurities in the water, and preventing accidents when oxygen is removed from the water.
    The proposed method for removing oxygen from water involves the steps of adding hydrazine to a dissolved oxygen fluid, passing a liquid through a layer of activated carbon to catalyze the reaction of dissolved oxygen with hydrazine, which results in coal impurities entering the fluid, and removing these impurities.
    Removal of unreacted and remaining in the liquid after catalyzing hydrazine is carried out by passing the liquid through a mixed layer of ion exchange resins based on a strongly basic anion exchanger and a strong acid cation exchanger. The process of removing oxygen with hydrazine using activated carbon as a catalyst is carried out on a mobile platform and involves additional operations of transporting the apparatus to a regeneration station for regeneration.
    The presence of coal impurities is due to the fact that, when passing through the coal layer, the liquid washes them out of the coal layer. These impurities may contain a wide variety of substances that are incompatible with the requirements imposed on high-quality oxygen-free liquid. In the manufacture of activated carbon, a wide variety of substances are used.
    carbon raw materials such as wood, coal, nutshells, petroleum coke. Therefore, the composition of the impurities depends on which raw materials are used to produce activated carbon. Regardless of the raw materials used, impurities also include coal particles.
    If necessary, obtain an oxygen-free liquid, free from
    5 unreacted hydrazine, an ion exchange resin containing a mixed resin layer is used to remove it. When using a resin blend layer, it can contain any commercially available cation exchange resin, for example Topas-C-249, and any commercially available basic anion exchange resin, for example Topas ASB-1.
    The ion exchange resin is not capable of filtering all coal particles contained in oxygen-free water. To completely remove them, install a mechanical filter with filter media. The particle size of the filter medium is chosen in such a way as to exclude the passage of coal particles.
    In a preferred embodiment, the removal of coal particles is also carried out by pre-washing
    5 activated carbon Activated carbon can be washed with uncommitted water, but the minerals contained in water are usually absorbed by coal and are contaminants.
    0 Selecting a resin blend for a layer allows both unreacted hydrazine and certain coal impurities to be removed.
    The method also provides for the incomplete removal of unreacted hydrazine followed by the addition of the desired amount.
    If the amount of unreacted hydrazine measured by the analyzer is less than the target for the output stream, sufficient hydrazine is used to obtain the target value used as a corrosion inhibitor,
    Use of hydrazine is associated with
    5, a hazard whose certainty is retained even when hydrazine is in the form of an aqueous solution. For example, by passing a hydrazine solution through an activated carbon layer and ion exchange resin layers in the layers,
    retain residual unreacted hydrazine, which may be hazardous to the health of personnel working with resin layers. Such a danger is increased for inexperienced operators working in the application zone of an oxygen-free fluid.
    The method allows to reduce or eliminate the danger caused by the use of hydrazine in the process. In this embodiment, an apparatus for purifying water from oxygen is installed on a movable closed platform.
    A movable closed platform allows the apparatus containing hydrazine and its associated apparatus to be separated from the main structure.
    At the same time, after purification of a certain amount of water from oxygen, if regeneration or replacement of activated carbon or resins is necessary, the platform can be transported to a regeneration station, where regeneration is carried out by specialists using specialized equipment, which allows the maintenance personnel to avoid contact with hydrazine vapors.
    Example 1. In accordance with the proposed method, oxygen is removed from a stream of 8 to 10 ppm dissolved oxygen flowing from the two-stage smart cooler. A flow at a rate of 416–2040 l / min, and typically 1900 l / min, is fed to a device containing a pump for hydrazine, six vessels connected to an activated carbon parallel to the parallel and six vessels connected to a parallel layer with a mixed bed.
    A 35% hydrazine solution is introduced into the stream at a rate of 1.5 l / h at 378 l / min of this stream. During the first 3.5 hours, the resulting product contains less than 0.1 ppm dissolved oxygen, and the flow rate of the hydrazine solution gradually decreases to 0.76 l / h per 378 l / min flow.
    After 36 hours of operation under the specified conditions, the consumption of the hydrazine solution is gradually reduced to 0.57 l / h. An experiment to this example shows that an average of about 8.9 ppm of hydrazine is introduced into the stream is sufficient.
    After the hydrazine solution is introduced into the stream, it is passed through vessels with activated carbon. Each vessel contains a layer of activated carbon with a volume of 1.7 m3, and the total volume of coal in all vessels is 10 m3. The stream is then passed through the vessels through the resin layers, each of which contains a layer of resin mixture
    2.7 m and the total volume of the resin mix is 16.2 m.
    Obtained according to Example 1, the product cleared and oxygen-free of oxygen contained less than 10 ppb of dissolved oxygen and less than 1 ppb of hydrazine. After the device was turned off for a long time with the resumption of its operation, a relatively high content of dissolved oxygen was found, however, this increased content was compensated by a temporary increase in hydrazine consumption.
    Example 2. Oxygen is removed either from condensate or from softened prepared water containing from 0.5 ppb to 10 ppb dissolved oxygen, the conductivity of which is 1 micron. The stream is treated in a device containing a pump for hydrazine. , three paralleled vessels with activated carbon and three vessels paired in parallel with layers of a mixture of resins, as well as a device for continuous measurement of the amount of oxygen.
    The flow rate to the device is 492-1780 L / min. The content of oxygen in the stream varies from maximum (a few ppm) when using softened prepared water to a minimum (less than 1 ppm) when processing condensate.
    When a stream is introduced into the device, a 35% hydrazine solution is pumped into it. During the first 24 hours, the flow rate of the hydrazine solution is 0.75 L / h per 378 L / min feed. The next 24 hours, the flow is gradually reduced to the minimum, i.e. 0.075 l / h per 378 l / min flow with dissolved oxygen in the amount of 1 ppm. The stoichiometric ratio was 0.064 L / h of a hydrazine solution per 378 L / min of a stream containing 1 ppm of dissolved oxygen.
    After entering into the stream of hydrazine, the mixture is passed through three vessels with activated carbon, 1.7 m of coal each. Consequently, the total volume of activated carbon is 5.04 m, and then the condensate is passed through three layers, the total volume of which was (2.7 cubic meters each), a mixture of 288 cubic feet of resin (8.1 m). A continuous device measures the amount of dissolved oxygen in the treated stream, after which the stream is passed to a storage tank. The content of dissolved oxygen in the treated medium was found to be from 2 to 19 ppb. After passing through carbon vessels, the flow conductivity is 6 µm, and after passing through the resin mixture, it decreases to a value below 1 µm, and usually to 2 µm.
    Ф о рм ул а and з о б р r ete n and
    权利要求:
    Claims (5)
    [1]
    1. A method of removing oxygen from water by contacting water previously treated with hydrazine with an activated carbon layer, characterized in that, in order to enable the use of deoxygenated water in a closed circulation system, due to the flexible regulation of unreacted hydrazine in water, the water after activated coal is passed through a layer of mixed-effect ion exchangers based on a strongly acidic cation exchanger and a strongly basic anion exchanger.
    [2]
    2. A method according to claim 1, characterized in that the water after the layer of ion exchangers of mixed action is additionally passed through a mechanical filter.
    [3]
    3. A method according to claim 1, characterized in that, in order to reduce the content of carbon impurities in water, activated carbon is previously subjected to backwashing with softened water.
    [4]
    A. The method according to claim 1, wherein in the circulation of the deoxygenated water at elevated temperatures, an additional amount of hydrazine is added to the water after passing it through a layer of ion exchangers of mixed action as a corrosion inhibitor.
    [5]
    5. A method according to claim 1, characterized in that, in order to prevent accidents when oxygen is removed from the water, the activated carbon layer and the mixed-action ion exchanger layer are mounted on a movable platform for transportation to the regeneration station.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1757455A3|1992-08-23|Method of removing oxygen from water
    KR100784438B1|2007-12-11|apparatus and method for continuous electrodeionization
    US4141828A|1979-02-27|Process for treating waste water
    US6372143B1|2002-04-16|Purification of produced water from coal seam natural gas wells using ion exchange and reverse osmosis
    US5374357A|1994-12-20|Filter media treatment of a fluid flow to remove colloidal matter
    CN102107988B|2013-06-12|Phenol-amine wastewater treatment and recycling method and device
    US10661220B2|2020-05-26|Hydrogen sulfide removal process
    CN102149642A|2011-08-10|Process for the recovery of water and valuable organics from wastewater in the production of aromatic carboxylic acids
    CN101773749B|2012-08-22|Method for purifying polyol for preventing natural gas from freezing and dehydrating natural gas and equipment
    CN101544430B|2011-06-08|Secondary treatment method of coking wastewater
    US4818411A|1989-04-04|Deoxygenation process
    JPH06207514A|1994-07-26|Apparatus and method of regenerating coolant for engine
    EP2291330B1|2013-07-03|Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction by means of ion exchange resins
    CN202148224U|2012-02-22|Ammonia-nitrogen wastewater treatment device and system
    Mackinnon et al.2003|Nutrient removal from wastewaters using high performance materials
    CN210528712U|2020-05-15|Processing system that high difficult degradation organic matter waste water discharged all up to standard
    Stetter et al.2002|Pilot scale studies on the removal of trace metal contaminations in drinking water treatment using chelating ion-exchange resins
    CN205773958U|2016-12-07|A kind of coking wastewater deep treatment device
    CN102476888A|2012-05-30|Treatment method and treatment equipment for coking wastewater
    CN210193715U|2020-03-27|Sulfolane purification treatment system
    US10029249B1|2018-07-24|System and method for ion exchange regeneration
    JP3344735B2|2002-11-18|Treatment of aqueous liquid for electric discharge machining
    US20150129503A1|2015-05-14|Ion exchange process with plug flow conditions and short residence times
    CN112624407A|2021-04-09|Deep purification method and device for oilfield acidizing and fracturing wastewater
    Matsumoto et al.1992|Physicochemical processes
    同族专利:
    公开号 | 公开日
    AT50971T|1990-03-15|
    BR8407220A|1985-11-26|
    JPH0502399B2|1993-01-12|
    NO853154L|1985-08-09|
    FI89258B|1993-05-31|
    JPS61500713A|1986-04-17|
    WO1985002605A1|1985-06-20|
    US4556492A|1985-12-03|
    AU3744585A|1985-06-26|
    DK365285A|1985-08-12|
    FI853154A0|1985-08-16|
    FI853154L|1985-08-16|
    NO167189B|1991-07-08|
    DK365285D0|1985-08-12|
    FI89258C|1993-09-10|
    DK162936B|1991-12-30|
    EP0167569A1|1986-01-15|
    EP0167569B1|1990-03-14|
    DE3481605D1|1990-04-19|
    NO167189C|1991-10-16|
    AU566615B2|1987-10-22|
    EP0167569A4|1987-04-10|
    DK162936C|1992-05-25|
    CA1248645A|1989-01-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2655141C1|2017-01-13|2018-05-23|Олег Владимирович Кленин|Method of removing oxygen from water|BE629884A|1963-03-22|
    US3604821A|1969-08-13|1971-09-14|Mc Donnell Douglas Corp|Stirling cycle amplifying machine|
    US3764548A|1971-09-13|1973-10-09|Petrolite Corp|Oxygen scavenger and use thereof|
    US3736253A|1972-04-10|1973-05-29|Sobin Chlor Alkali Inc|Process and apparatus for removing mercury from waste water|
    GB1362736A|1972-06-30|1974-08-07|Otsuka Kagaku Yakuhin|Composition for removing oxygen from water and method therefor|
    US3962113A|1972-12-26|1976-06-08|Olin Corporation|Method for accelerating oxygen removal employing an aqueous solution of an alkyl hydrazine|
    DE2341363C3|1973-08-16|1979-05-31|Kali-Chemie Ag, 3000 Hannover|Process for the preparation of a catalyst for the decomposition of hydrazine and its derivatives|
    US3913339A|1974-03-04|1975-10-21|Hughes Aircraft Co|Reduction in cooldown time for cryogenic refrigerator|
    US4218315A|1974-07-29|1980-08-19|Hartkorn Karl Heinz|Oxidation and adsorption method for removing contaminating substances from liquids|
    FR2297814B1|1975-01-20|1978-07-21|Ugine Kuhlmann|
    US4098691A|1977-02-10|1978-07-04|Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources|Purification of water for boiler|
    US4287072A|1979-10-18|1981-09-01|Drew Chemical Corporation|Water treatment by ion exchange resin|
    DD149794A1|1980-03-10|1981-07-29|Jochen Karthe|METHOD FOR SEPARATING HYDRAZINE|
    US4269717A|1980-04-17|1981-05-26|Nalco Chemical Company|Boiler additives for oxygen scavenging|
    US4397155A|1980-06-25|1983-08-09|National Research Development Corporation|Stirling cycle machines|
    US4289645A|1980-07-14|1981-09-15|Betz Laboratories, Inc.|Hydroquinone and mu-amine compositions|
    US4363734A|1981-02-05|1982-12-14|Nalco Chemical Company|1,3-Dihydroxy acetone as an oxygen scavenger for water|
    US4383920A|1981-05-29|1983-05-17|Ecolochem, Inc.|Mobile fluid purification system|
    US4399098A|1981-09-21|1983-08-16|Dearborn Chemical Company|Prevention of corrosion in aqueous solutions|US4818411A|1983-12-16|1989-04-04|Ecolochem, Inc.|Deoxygenation process|
    DK8600502A|1985-02-05|1986-08-06|
    US4627921A|1985-04-29|1986-12-09|L A Water Treatment Corporation|Treatment of water to lower the oxygen and the total organic carbon within the same|
    JPS6345474B2|1985-05-28|1988-09-09|Kurita Water Ind Ltd|
    US4629571A|1985-09-11|1986-12-16|The Graver Company|Deoxygenation and purification of liquids|
    US4851130A|1988-11-30|1989-07-25|Pfizer Inc.|Oxygen removal with carbon catalyzed erythorbate or ascorbate|
    US5108624A|1990-03-12|1992-04-28|Arrowhead Industrial Water, Inc.|Method for deoxygenating a liquid|
    US5362408A|1992-07-14|1994-11-08|The Western Company Of North America|High temperature gel stabilizer for fracturing fluids|
    US5500185A|1994-07-29|1996-03-19|Southern California Edison|Deoxygenation process|
    US5785857A|1996-04-30|1998-07-28|Mobile Process Technology, Inc.|Mobile process for the recovery of spent heat transfer fluids|
    KR100317527B1|1999-10-22|2002-01-18|이종훈|Dissolved Oxygen Removal Apparatus by Electrochemical Catalytic Reaction and Method Thereof|
    CA2481540C|2002-04-08|2010-06-15|Dominion Engineering, Inc.|Liquid degassing system for power plant system layup|
    US7851406B2|2007-06-12|2010-12-14|Korea Institute Of Chemical Technology|Nano-sized palladium-doped cation exchange resin catalyst, preparation method thereof and method of removing dissolved oxygen in water using the same|
    US9315736B2|2010-12-16|2016-04-19|Energia Technologies, Inc.|Methods of fuel production|
    CN103459031A|2010-12-16|2013-12-18|能源技术公司|Catalysts, methods of preparation of catalyst, methods of deoxygenation, and systems for fuel production|
    RU2566146C2|2011-05-17|2015-10-20|Инфилко Дегремон, Инк.|Method and plant for processing of water and effluents|
    US11156041B2|2012-02-22|2021-10-26|Richard Paul Posa|System and method for treating water|
    US10370272B2|2016-03-02|2019-08-06|Cameron Solutions, Inc.|Subsea deoxygenation in a water injection process plant|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/562,001|US4556492A|1983-12-16|1983-12-16|Deoxygenation process|
    [返回顶部]