GB2110949A - The catalytic oxidation of deuterium into heavy water - Google Patents

The catalytic oxidation of deuterium into heavy water Download PDF

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Publication number
GB2110949A
GB2110949A GB08232651A GB8232651A GB2110949A GB 2110949 A GB2110949 A GB 2110949A GB 08232651 A GB08232651 A GB 08232651A GB 8232651 A GB8232651 A GB 8232651A GB 2110949 A GB2110949 A GB 2110949A
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GB
United Kingdom
Prior art keywords
deuterium
heavy water
combustion
flow
beds
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.)
Withdrawn
Application number
GB08232651A
Inventor
Hansjorg Pfeiffer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sulzer AG
Original Assignee
Sulzer AG
Gebrueder Sulzer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sulzer AG, Gebrueder Sulzer AG filed Critical Sulzer AG
Publication of GB2110949A publication Critical patent/GB2110949A/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B4/00Hydrogen isotopes; Inorganic compounds thereof prepared by isotope exchange, e.g. NH3 + D2 → NH2D + HD
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00265Part of all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2208/00274Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/021Processes carried out in the presence of solid particles; Reactors therefor with stationary particles comprising a plurality of beds with flow of reactants in parallel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Apparatus for the catalytic oxidation of deuterium to form heavy water comprises a number of stages of solid catalyst beds (1, 1', 1'') which are connected in series for the flow of oxygen-containing gas, e.g. air, from 5, and which are in parallel with one another for the inflowing deuterium from 2 to be introduced via 3, 3', 3''. Disposed in the flow path of the combustion product after each catalyst bed (1, 1', 1'') is a cooler (6, 6', 6'') in which the heat of combustion evolved in the previous catalyst bed (1, 1', 1'') is transferred to a coolant. <IMAGE>

Description

SPECIFICATION The catalytic oxidation of deuterium into heavy water This invention relates to apparatus and a method for the catalytic oxidation of deuterium into heavy water.
To produce heavy water, deuterium as a starting material is prepared in a very wide variety of concentration processes from hydrogen, hydrogen compounds and mixtures containing hydrogen; the deuterium may be present, for instance, as the sole component or for instance, in a monothermal ammonia process- it may be present as a component of a mixture of dueterium and nitrogen.
Deuterium can be oxidized with a combustionsupporting gas, such as dry air, in an open-flame burner to form heavy water. In this process the high flame temperature leads to the formation of nitrogen oxides and, therefore, to heavy nitric acid (DNO3) which it is essential to separate from the heavy water before the heavy water is used in a nuclear reactor.
Another substantial disadvantage of these procedures is their uncertain operaiton. For instance, the burners can be operated only in a narrow range. If, for instance, the preceding deuterium preparation plant has to be run on partial load for any reason, the flame may go out.
It is also known to oxidize deuterium catalytically to form heavy water. To prevent overheating and destruction of the catalyst, the reaction must be performed with a very substantial excess of combustion-supporting gas. Also, the explosion limit of deuterium in such gas must not be exceeded (approximately 4.9 volume per cent in air).
Consequently, there is only a reduced concentration of heavy water in the combustion-supporting gas at the catalyzer exit, and so elaborate facilities must be provided to separate out the heavy water by condensation and freezing or an elaborate absorption process is necessary.
The present invention provides, according to one aspect, apparatus for the catalytic oxidation of deuterium to form heavy water by means of a combustion-supporting gas which is supplied in excess and which consists of oxygen or a gas mixture, more particularly air, containing oxygen as an ingredeient, the apparatus comprising at least two solid catalyst beds (1, 1', 1"), connections (11', 11") to provide for the flow of the combustion-supporting gas in series through the beds, parallel connections (3, 3', 3") to the catalyst beds for the deuterium flow, and a cooler (6, 6', 6") downstream of each catalyst bed for the removal of the heat of the oxidation reaction by means of a coolant.
By means of the invention, it is possible to construct apparatus in which the heavy water produced by oxidation is present in a high concentration in the combustion-supporting gas, usually dried air, and can be separated quite simply by condensation, in which the formation of nitrogen oxides is inhibited and in which the deuterium concentration is outside the explosion limit.
Advantageously, a catalyst consisting of a noble metal is used, such as palladium on aluminium oxide pellets or spheres as substrate.
Because of the manner in which, according to the invention, the catalyst beds are connected and coolers are interposed, the temperature at which the deuterium enters the various catalyst beds can be maintained at least substantially constant.
The present invention also provides, according to a second aspect, a method of catalytically oxidising deuterium to form heavy water in which deuterium is supplied in parallel to each of at least two solid catalyst beds while a combustion-supporting gas consisting of or containing oxygen is passed in series through the beds and, downstream of each bed, through a cooler in which the heat of the oxidation reaction in the preceding bed is removed.
The invention may be carried into practice in various ways but one form of apparatus and its mode of operation in accordance with the invention will now be described by way of example with reference to the single figure of the accompanying drawing which shows the apparatus diagrammatically.
The drawing shows a series of three catalyst beds 1, 1', 1". Deuterium our a mixture thereof with nitrogen is supplied to the oxidation apparatus through a main 2. Branching off therefrom are branch lines 3, 3', 3" comprising control valves 4, 4', 4" respectively.
A combustion-supporting gas, such as dry air, is introduced into the first bed 1 of the oxidation apparatus in excess through a line 5, first being mixed with gas arriving through the first branch line 3 and consisting of deuterium alone or with nitrogen.
The mixture resulting from the reaction of the two components in the first bed 1 passes into a cooling coil 6 in which the heat of combustion is removed by indirect heat exchange with cooling water.
The combustion product is reccoled to entry temperature in the coil 6, then goes through a line 11', and-after receiving an admixture through branch line 3' of substantially the same quantity of deuterium or of a gas mixture of deuterium and nitrogen as in the case of branch line 3 - passes into the second catalyst bed 1 ' for further oxidation of the deuterium. The heat of combustion is removed from the combustion product in a cooling coil 6' and the mixture then goes through a line 11", and after an admixture again of the same quantity of deuterium gas or of a mixture of deuterium and nitrogen by way of branch line 3" - passes into the third catalyst bed 1" for oxidation.
In the apparatus being described, the oxidation apparatus consists of three stages; the quantity of deuterium fed to the apparatus has by the time it reaches the exit from the third stage been oxidized at least substantially completely into heavy water. Of course the apparatus can comprise a relatively large number of stages, in which event the heavy-water content of the combustion-supporting gas can be increased to near its dew point.
The end product discharged from the third stage is recooled in the coil 6" to at least the entry tempera ture of, for example, 1 00 C and removed from the apparatus through a line 12. In a manner which is not shown, heavy water is then condensed from the combustion product consisting of a mixture of heavy water vapour, the remainder of the combustion-sup porting gas and, possibly, inert components present in the deuterium supply. Previously to this, traces of gas impurities are removed by ion exchange.
The quantities of deuterium supplied to the various catalyst beds can be varied by means of the valves 4, 4', 4" in the respective lines 3, 3', 3". This is advantageous because the specific heat capacity of the combustion product increases as a result of decreasing deuterium content and increasing heavy water vapour content. Consequently, an increased addition of deuterium is possible in later stages and the apparatus can comprise fewer stages.
In the apparatus described, the cooling coils 6, 6', 6" are disposed in a tank 7 through which cooling water flows. Cooling water is supplied to the tank 7 through a line 8 by means of a pump 9 and is discharged through a line 10.
The cooling system 7 could alternatively comprise separate coolers each associated with one catalyst bed. Instead of water, the coolant could be, for instance, oil or cooled air or some other coolant. The coolant entry temperature is adjusted to obviate condensation of the heavy water vapour during recooling.

Claims (6)

1. Apparatus for the catalytic oxidation of deuterium to form heavy water by means of a combustion-supporting gas which is supplied in excess and which consists of oxygen or a gas mixture, more particularly air, containing oxygen as an ingredient, the apparatus comprising at least two solid catalyst beds (1, 1', 1"), connections (11', 11") to provide for the flow of the combustion-supporting gas in series through the beds, parallel connections (3, 3', 3") to the catalyst beds for the deuterium flow, and a cooler (6, 6', 6") downstream of each catalyst bed for the removal of the heat of the oxidation reaction by means of a coolant.
2. Apparatus as claimed in Claim 1 in which the connections (3, 3', 3") for the deuterium flow include respective flow-controlling means (4, 4', 4").
3. Apparatus as claimed in Claim 1 or Claim 2 in which all the coolers are disposed in a common casing with an inlet and outlet for the flow through the casing of a liquid coolant.
4. Apparatus for the catalytic oxidation of deuterium constructed and arranged to operate substantially as described herein with reference to the accompanying drawing.
5. A method of catalytically oxidising deuterium to form heavy water in which deuterium is supplied in parallel to each of at least two solid catalyst beds while a combustion-supporting gas consisting of or containing oxygen is passed in series through the beds and, downstream of each bed, through a cooler in which the heat of the oxidation reaction in the preceding bed is removed.
6. A method of catalytically oxidising deuterium substantially as described herein with reference to the accompanying drawing.
GB08232651A 1981-12-08 1982-11-16 The catalytic oxidation of deuterium into heavy water Withdrawn GB2110949A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH7829/81A CH648270A5 (en) 1981-12-08 1981-12-08 DEVICE FOR CATALYTIC OXIDATION FROM DEUTERIUM TO HEAVY WATER.

Publications (1)

Publication Number Publication Date
GB2110949A true GB2110949A (en) 1983-06-29

Family

ID=4331072

Family Applications (1)

Application Number Title Priority Date Filing Date
GB08232651A Withdrawn GB2110949A (en) 1981-12-08 1982-11-16 The catalytic oxidation of deuterium into heavy water

Country Status (3)

Country Link
CH (1) CH648270A5 (en)
DE (1) DE3231335A1 (en)
GB (1) GB2110949A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9670064B1 (en) * 2012-09-27 2017-06-06 Consolidated Nuclear Security, LLC Production of heavy water

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9670064B1 (en) * 2012-09-27 2017-06-06 Consolidated Nuclear Security, LLC Production of heavy water

Also Published As

Publication number Publication date
DE3231335A1 (en) 1983-07-21
CH648270A5 (en) 1985-03-15

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