CN109455669B - System and method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water - Google Patents
System and method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water Download PDFInfo
- Publication number
- CN109455669B CN109455669B CN201811216421.2A CN201811216421A CN109455669B CN 109455669 B CN109455669 B CN 109455669B CN 201811216421 A CN201811216421 A CN 201811216421A CN 109455669 B CN109455669 B CN 109455669B
- Authority
- CN
- China
- Prior art keywords
- water
- deuterium
- separation
- column
- enriched
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B5/00—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/02—Separation by phase transition
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a system for separating natural water to prepare deuterium depleted water and deuterium enriched water, which is characterized in that the core of the system is a closed loop formed by sequentially connecting a plurality of separation columns end to end, and the system also comprises a raw material water storage tank, a deuterium enriched water storage tank, a deuterium depleted water storage tank, a metering pump, a vaporizer, and a pipeline and a valve for connecting the raw material water storage tank, the deuterium enriched water storage tank, the deuterium depleted water storage tank, the metering pump and the vaporizer. The method adopts a simulated moving bed principle to carry out separation, raw material water vapor circularly moves in a closed loop formed by separation columns through sequential heating/cooling of the separation columns and control of a one-way valve, a continuously increased deuterium concentration gradient is obtained along with increase of circulation times, the separation columns extract deuterium-enriched water from the tops of the separation columns at the near ends of the heating loops after heating and cooling circulation for a certain number of times, and extract deuterium-depleted water from the bottoms of the separation columns at the far ends of the heating loops. The semi-continuous deuterium separation device has the advantages of simple structure, low-cost filling material, convenience in control, smaller equipment scale and lower construction cost, and can be used for directly separating natural water in a semi-continuous mode to prepare deuterium-depleted water and deuterium-enriched water.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a system and a method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water.
Background
Deuterium-depleted water is water with deuterium content of less than 150ppm, and passes through Gabor Somlyai, Honkgarian scientist, Guanbanbo, Japan Shennachuan university, etcThe experiments of (2) prove that the deuterium-depleted water has various biological effects beneficial to human bodies: activating human body cells, enhancing human body immunity, preventing cancer and protecting health. Deuterium-depleted water is an important auxiliary product combined with cancer treatment internationally at present, and some conditional countries in the world are dedicated to research and development of deuterium-depleted water, such as Japan, America, Romania and the like, and products are put on the market, and the application of deuterium-depleted water in the field of cancer treatment is advanced. Heavy water (D) having a high deuterium content2O) also have extremely important applications. Heavy water can be used as a moderator of a nuclear reactor, the neutron speed is reduced, and the nuclear fission process is controlled; heavy water is a valuable tracer in the study of chemical and physiological changes, such as the determination of water metabolism in plants and animals; in addition, if the subject of the nuclear magnetic resonance analysis is hydrogen, heavy water is also used as a solvent.
Raw materials for producing the deuterium-depleted water and the heavy water are natural water with rich resources and low price, and the conventional methods for producing the deuterium-depleted water and the heavy water mainly comprise a high-tower layered distillation method and a water/hydrogen double-temperature exchange method. Distillation methods are based on natural water with multiple components (e.g. H)2O, HDO, and a very small amount of D2O) different volatility, hydrogen isotope separation can occur during coexistence of gas and liquid phases. During the steam rising process, H2The O is gradually enriched at the top of the column due to its high volatility, and the liquid is gradually overflowed to the bottom of the column, HDO (including a very small amount of D)2O) is gradually enriched at the bottom of the column due to low volatility, the water distillation method has the advantages of no need of using catalyst or chemical reagent, simple and mature production process, small separation coefficient of about 1.03-1.06, high equipment size, complexity and large construction investment due to the need of connecting a plurality of separation stages in series, large water amount to be treated in the production process due to the need of repeated condensation and vaporization, high energy consumption and high operation costI.e. deuterium is transferred from the liquid phase into the gas phase. Thus, the low-temperature main tower, namely the cold tower, is used for enrichment, and the high-temperature auxiliary tower, namely the hot tower, is used for phase conversion, so that water is depleted to form deuterium-depleted water. However, the industrial application of the water/hydrogen double temperature exchange method has the following problems: on one hand, the cold tower must use expensive platinum-based hydrophobic catalyst as filler, and the system construction cost is high; on the other hand, the exchange reaction of the water/hydrogen isotopes comprises two continuous processes of liquid phase catalytic exchange and vapor phase catalytic exchange, and the control of parameters such as temperature, flow and the like is complex.
Japanese research shows that silica gel, activated alumina and 5A molecular sieve are used as fillers for tritiated water (HTO) and light water (H) in a fixed bed carrier gas circulation mode2O) has a separating effect. However, the existing water separation research adopting the inorganic filler only adopts a small-scale fixed bed carrier gas purging mode, a large amount of water residues exist in the molecular sieve filler after the bed body penetrates, the molecular sieve filler can be reused only by carrying out complex regeneration treatment, the separation efficiency is low, and the method has no practical application value.
Disclosure of Invention
Based on the problems, the invention provides a system for separating natural water to prepare deuterium depleted water and deuterium enriched water, compared with the traditional distillation method and a double-temperature exchange method, the system has the advantages of simple structure, low-cost filling materials, convenient control, smaller equipment scale and lower construction cost, and can directly separate the natural water in a semi-continuous mode to prepare the deuterium depleted water and the deuterium enriched water.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a system for separating natural water to prepare deuterium depleted water and deuterium enriched water comprises a sealed electric heating box, a separation component arranged in the electric heating box, a raw material water storage tank, a deuterium enriched water storage tank and a deuterium depleted water storage tank, wherein the raw material water storage tank, the deuterium enriched water storage tank and the deuterium depleted water storage tank are arranged outside the electric heating box; the separation assembly comprises No. 1-n separation columns which are connected in series to form a closed loop, and adjacent separation columns are connected through a pipeline provided with a one-way valve; the raw material water storage tank is provided with a raw material water inlet pipe, the raw material water inlet pipe penetrates through the electric heating box, the raw material water inlet pipe outside the electric heating box is provided with a metering pump, the raw material water inlet pipe inside the electric heating box is provided with a vaporizer, and the upper ends of the No. 1-n-1 separation columns are respectively connected with a raw material water inlet pipe pipeline through No. 1-n-1 feeding valves corresponding to the No. 1-n-1 separation columns; the deuterium-enriched water storage tank is provided with a deuterium-enriched water pipe, the deuterium-enriched water pipe penetrates through the electric heating box, and the upper end of the No. 1 separation column is communicated with the deuterium-enriched water pipe through a deuterium-enriched water valve; the deuterium depleted water storage tank is provided with a deuterium depleted water pipe, the deuterium depleted water pipe penetrates through the electric heating box, and the lower end of the n-number separation column is communicated with the deuterium depleted water pipe through a deuterium depleted water valve.
The vacuum pump is provided with a vacuum tube, the vacuum tube penetrates through the electric heating box, and the lower ends of the No. 1-n separation columns are respectively connected with vacuum tube pipelines through No. 1-n vacuum valves corresponding to the No. 1-n separation columns.
Specifically, the electric heating box is a phenolic foam plate box body, a dry-burning type electric heating rod is arranged at the bottom of the electric heating box, and the temperature in the box body is not lower than 100 ℃.
Preferably, the separation column adopts molecular sieve as a filler.
As a preferred scheme, the separation column is a stainless steel pipe with phi 50-phi 250, a stainless steel end enclosure is welded on the end surface of the separation column, a stainless steel corrugated pipe with phi 10-phi 20 is connected, and the corrugated pipes are connected by adopting a cutting sleeve or a welding mode.
Preferably, the outer wall of the separation column is wrapped by a stainless steel mica thin-wall annular heating ring, so that the rated service temperature is not lower than 500 ℃.
Preferably, the metering pump is a diaphragm pump.
Further, the vaporizer is a stainless steel spiral coil which is arranged in the heating furnace, liquid water enters the spiral pipe in a high-temperature state and is directly changed into steam through heating vaporization, and liquid water is not retained.
Furthermore, the vacuum pump is a combination of a water ring pump and a rotary vane pump, the front stage is the water ring pump, and the rear stage is the rotary vane pump with a gas ballast valve.
The invention also provides a method for preparing the deuterium-depleted water and the deuterium-enriched water by using the system, the method can directly separate the natural water in a semi-continuous mode to prepare the deuterium-depleted water and the deuterium-enriched water, and the method has the advantages of simple operation, high separation efficiency and good separation effect.
A method for preparing deuterium-depleted water and deuterium-enriched water using the above system, comprising the steps of:
s1: setting the internal temperature of the electric heating box to be more than 100 ℃, starting a heating ring outside the separation columns to increase the temperature of each separation column to be more than 300 ℃, vacuumizing to remove residual water vapor in the separation columns, and then reducing to 100 ℃;
s2: natural water in a raw material water storage tank is pumped by a metering pump, and then is converted into water vapor by a vaporizer, and then enters a No. 1-n-1 separation column;
s3: starting a heating ring to enable the temperature of the No. 1 separation column to rise to more than 300 ℃, desorbing water vapor in the No. 1 separation column, enabling the pressure in the column to rise, enabling the water vapor to move backwards to enter the No. 2 column when the pressure of the check valve is exceeded, further enabling the water vapor of the No. 2 column to enter the No. 3 column through the check valve, enabling the subsequent separation columns to sequentially perform the process, finally enabling the water vapor in the No. 1-n-1 separation column to completely enter the No. 2-n separation column, finishing the first rearrangement, gradually reducing the concentration of deuterium in the water vapor along No. 2 → n, vacuumizing to remove residual water vapor of the No. 1 column to regenerate the separation column when the pressure in the No. 1 separation column is not obviously changed, and simultaneously closing the No. 1 column heating ring;
s4: when the temperature of the No. 1 column is reduced to 100 ℃, starting the No. 2 column for heating, desorbing water vapor and moving backwards under the driving of pressure difference, wherein the water vapor completely enters the No. 3-n and No. 1 separation columns to finish the second rearrangement; after the desorption of the No. 2 column is finished, the No. 2 column regeneration and the No. 3 column desorption are carried out according to the same mode; the subsequent separation column operation is analogized in turn; after the n separation column is desorbed, the water vapor is rearranged for the n time, and the water vapor is distributed on the 1 to n-1 separation columns again, which indicates that the system completes one cycle separation;
s5: connecting a deuterium-enriched water storage tank pipeline, starting a heating ring to heat the No. 1 separation column, and discharging and collecting deuterium-enriched water from the top of the No. 1 separation column; connecting a pipeline of a deuterium depleted water storage tank, heating the n-1 separation column, and discharging and collecting deuterium depleted water from the bottom of the column; then, raw material water is injected from the middle section of the separation loop, and then the next circulation separation operation can be carried out.
Compared with the prior art, the invention has the following beneficial effects:
(1) the system for preparing the deuterium-depleted water and the deuterium-enriched water by separating the natural water adopts a simulated moving bed principle, and utilizes the sequential heating/cooling of the separation columns and the control of the one-way valve, raw material water vapor circularly moves in a closed loop formed by the separation columns to obtain a deuterium concentration gradient, the deuterium concentration at the near end of the loop for heating desorption is highest, the deuterium concentration at the far end is gradually reduced, and the deuterium concentration gradient is continuously increased along with the increase of the adsorption/desorption times of the separation columns. Heating the separation column at the near end of the loop after the separation column is heated and cooled for a certain number of times, and extracting deuterium-enriched water from the top of the column; heating a separation column at the far end of the loop, and extracting the deuterium depleted water from the bottom of the column; then, raw material steam with the same extraction amount is injected from the middle section of the loop, and the next stage of separation operation is carried out. Compared with the traditional distillation method and the double-temperature exchange method, the semi-continuous deuterium separating device has the advantages of simple structure, low-price filling materials, convenience in control, smaller equipment scale and lower construction cost, and can be used for directly separating natural water in a semi-continuous mode to prepare deuterium-depleted water and deuterium-enriched water.
(2) The separation method has flexible operation, can conveniently obtain the deuterium-depleted water and the deuterium-enriched water with different deuterium contents through process control, can obtain expected separation effect by adjusting the number of the separation columns or the circulating separation operation times, and has strong adaptability.
(3) The invention is based on the simulated moving bed technology, in the system of the invention, an adsorbent (namely a separation component) is fixed, and fluid (namely natural water vapor) continuously flows in a separation loop through the control of process parameters to generate a gas-solid phase reverse flow effect similar to a real moving bed; and the deuterium concentration gradient of the water vapor adsorption zone in the solid-phase molecular sieve is increased continuously along with the time, so that the separation of the deuterium-depleted water and the deuterium-enriched water is realized. The system not only has higher production capacity and separation efficiency than the traditional fixed bed, but also can avoid the abrasion of the real moving bed adsorbent, the blockage of fragments or dust soil or the channeling among solid particles.
(4) The invention creatively applies the simulated moving bed technology to the natureThe water is separated, and through the design of a closed-loop separation system, steam can continuously and circularly flow in a closed-loop separation loop and utilizes H under the condition of the temperature of more than 100 DEG C2O and HDO (and very small amount of D)2O) the difference of adsorption/desorption performances on the molecular sieve, realizes one-step efficient separation by taking natural water as a direct treatment object, obtains deuterium-depleted water and deuterium-enriched water simultaneously, can effectively reduce the preparation cost and expand the application field.
(5) The separation method adopts the accumulative cycle separation operation, the separation coefficient of hydrogen/deuterium in natural water is obviously greater than that of a distillation method, and compared with the traditional distillation method, the volume of equipment is obviously reduced, and the construction cost and the operation energy consumption can be greatly reduced; compared with a water/hydrogen double-temperature exchange method, the filling material is a molecular sieve with low price, a platinum-based noble metal catalyst is not needed, and the long-term service performance is stable, so that the system cost is greatly reduced.
(6) The working medium of the separation method is only water vapor with the temperature of about 100 ℃, the separation operation is carried out in a closed loop formed by a series of separation columns, and auxiliary media such as hydrogen and the like are not needed, so the separation method is simpler and more convenient to operate and has no safety risks such as burning explosion and the like.
(7) Because the raw material is natural water, the deuterium-enriched water can be obtained as the raw material for producing the heavy water while producing the poor deuterium, so that the preparation cost of the poor deuterium can be greatly reduced, and the application of the poor deuterium in the field of biological medicine can be promoted.
Drawings
FIG. 1 is a schematic diagram of the system of the present invention.
Wherein, the names corresponding to the reference numbers are:
1-separation column, 11-one-way valve, 2-vacuum pump, 21-vacuum tube, 22-vacuum valve, 3-raw material water storage tank, 31-raw material water inlet tube, 32-feed valve, 33-metering pump, 34-vaporizer, 4-deuterium-enriched water storage tank, 41-deuterium-enriched water tube, 42-deuterium-enriched water valve, 5-deuterium-depleted water storage tank, 51-deuterium-depleted water tube, and 52-deuterium-depleted water valve.
Detailed Description
The present invention will be further described with reference to the following description and examples, which include but are not limited to the following examples.
Examples
The present embodiment aims to provide a system for separating natural water to prepare deuterium-depleted water and deuterium-enriched water, which not only helps to solve the problem of high cost of preparing deuterium-depleted water by the existing distillation method and two-temperature exchange method, but also can simultaneously obtain deuterium-enriched water as a raw material for heavy water production.
A system for separating natural water to prepare deuterium depleted water and deuterium enriched water is shown in figure 1 and comprises a sealed electric heating box, a separation component arranged in the electric heating box, a raw material water storage tank 3, a deuterium enriched water storage tank 4, a deuterium depleted water storage tank 5 and a vacuum pump, wherein the raw material water storage tank 3, the deuterium enriched water storage tank 4, the deuterium depleted water storage tank 5 and the vacuum pump are arranged outside the electric heating box. The electric heating box is a phenolic foam plate box body, and a dry-burning type electric heating rod is arranged at the bottom of the electric heating box, so that the temperature in the box body is more than 100 ℃, and the water vapor is ensured not to be condensed into liquid water.
Specifically, the core of the system is a separation assembly, the separation assembly is a plurality of separation columns (No. 1-n, n is more than or equal to 2), the separation columns are sequentially connected through pipelines according to the number (No. 1 → No. 2 → … → n → No. 1) to form a closed loop, a one-way valve 11 for preventing water vapor from flowing back is further arranged on a pipeline between every two adjacent separation columns, the opening pressure difference of all the one-way valves is adjustable within the range of 0.1-0.5 MPa, and when the pressure in the columns exceeds a set value, the one-way flow can be conducted towards the separation columns at the rear section. The separation column adopts molecular sieves as fillers, such as 4A, 5A, carbon molecular sieves and the like, because the molecular sieve type fillers still have more than about 15 percent of water absorption rate at more than 100 ℃, have stable properties, cannot be pulverized in the adsorption/desorption process and can be used for a long time; the separation column is a stainless steel pipe with phi 50-phi 250, a stainless steel end enclosure is welded on the end surface of the separation column, the separation column is connected with stainless steel corrugated pipes with phi 10-phi 20, and the corrugated pipes are connected by adopting a cutting sleeve or a welding mode; and the outer wall of the separation column is wrapped by a stainless steel mica thin-wall annular heating ring, and the long-term use temperature can reach 500 ℃.
A raw material water inlet pipe 31 is arranged on the raw material water storage tank 3, the raw material water inlet pipe penetrates through the electric heating box, a metering pump 33 is arranged on the raw material water inlet pipe 31 outside the electric heating box, a vaporizer 34 is arranged on the raw material water inlet pipe in the electric heating box, the upper ends of the No. 1-n-1 separation columns are respectively connected with a raw material water inlet pipe pipeline through No. 1-n-1 corresponding feeding valves 32, natural water in the raw material water storage tank is extracted through the metering pump, and is converted into water vapor through the vaporizer to enter the No. 1-n-1 separation columns; the metering pump 33 is a diaphragm pump, and can perform two-dimensional adjustment on output flow through stroke and frequency, wherein the stroke is used for coarse adjustment of the flow, and the frequency is used for fine adjustment of the flow; the vaporizer 34 is a stainless steel spiral coil which is arranged in the heating furnace, liquid water enters the spiral pipe in a high-temperature state, is directly changed into steam by heating and vaporization, and liquid water is not retained, so that the steam flow is accurately controlled.
The deuterium-enriched water storage tank 4 is provided with a deuterium-enriched water pipe 41 which penetrates through the electric heating box, and the upper end of the No. 1 separation column is communicated with the deuterium-enriched water pipe through a deuterium-enriched water valve 42;
the deuterium depleted water storage tank 5 is provided with a deuterium depleted water pipe 51 which penetrates through the electric heating box, and the lower end of the n-number separation column is communicated with the deuterium depleted water pipe through a deuterium depleted water valve 52.
The vacuum pump 2 is provided with a vacuum tube 21 which penetrates through the electric heating box, and the lower ends of the No. 1-n separation columns are respectively connected with vacuum tube pipelines through No. 1-n vacuum valves 22 corresponding to the No. 1-n separation columns; the vacuum pump 2 is a combination of a water ring pump and a rotary vane pump, the front stage is the water ring pump, the rear stage is the rotary vane pump with a gas ballast valve, and high vacuum degree can be obtained under the condition of water vapor medium.
The embodiment also provides a method for preparing deuterium-depleted water and deuterium-enriched water by using the system, which specifically comprises the following steps:
s1: setting the temperature in a sealed electric heating box to be more than 100 ℃, starting a heating ring outside the separation columns to raise the temperature of each separation column to be more than 300 ℃, vacuumizing to remove residual water vapor in the separation columns, and then reducing to about 100 ℃;
s2: natural water in a raw material water storage tank is pumped by a metering pump, and then is converted into water vapor by a vaporizer, and then enters a No. 1-n-1 separation column;
s3: starting a heating ring to enable the temperature of the No. 1 separation column to rise to more than 300 ℃, desorbing water vapor in the No. 1 separation column, enabling the pressure in the column to rise, enabling the water vapor to move backwards to enter the No. 2 column when the pressure of the check valve is exceeded, further enabling the water vapor in the No. 2 column to enter the No. 3 column through the check valve, enabling the subsequent separation columns to sequentially perform the process, finally enabling the water vapor in the No. 1-n-1 separation column to completely enter the No. 2-n separation column, finishing the first rearrangement, gradually reducing the concentration of deuterium in the water vapor along No. 2 → n, vacuumizing to remove residual water vapor in the No. 1 column to regenerate the separation column when the pressure in the No. 1 separation column is not obviously changed (namely after the desorption is finished), and simultaneously closing the No. 1 column heating ring;
s4: when the temperature of the No. 1 column is reduced to about 100 ℃, starting the No. 2 column, heating to over 300 ℃, desorbing water vapor, moving backwards under the driving of pressure difference, and allowing all the water vapor to enter No. 3-n and No. 1 separation columns to finish secondary rearrangement; after the desorption of the No. 2 column is finished, the No. 2 column regeneration and the No. 3 column desorption are carried out according to the same mode, and the third rearrangement is finished; the subsequent separation column operation is analogized in turn; after the n separation column is desorbed, the water vapor is rearranged for the n time, and the water vapor is distributed on the 1 to n-1 separation columns again, which indicates that the system completes the circular separation;
s5: connecting a deuterium-enriched water storage tank pipeline, starting a heating ring to heat the No. 1 separation column, and discharging and collecting deuterium-enriched water from the top of the No. 1 separation column; and (4) connecting a pipeline of the deuterium-depleted water storage tank, heating the n-1 separation column, and discharging and collecting the deuterium-depleted water from the bottom of the column.
S6: performing deuterium content sampling analysis on water vapor in the No. 2 to (n-2) separation columns, selecting the separation columns with the deuterium content close to that of natural water, and injecting raw material water vapor from the tops of the separation columns, wherein the injection amount is equal to the extraction amount of the deuterium-depleted water and the deuterium-enriched water; then the next cycle of separation operation is performed.
If the deuterium concentration and extraction amount of the deuterium-enriched water and the deuterium-depleted water separated in one cycle do not reach the expected values, a larger deuterium concentration gradient can be obtained by increasing the number of the separation columns or the cycle times, so as to achieve the expected separation effect. Compared with the traditional distillation method and the double-temperature exchange method, the semi-continuous deuterium separating device has the advantages of simple structure, low-price filling materials, convenience in control, smaller equipment scale and lower construction cost, and can be used for directly separating natural water in a semi-continuous mode to prepare deuterium-depleted water and deuterium-enriched water.
The separation system and method of the present embodiment are described in detail below in two specific examples.
Example 1: single cycle mode, deuterium depleted water preparation with deuterium concentration of 80ppm
The core component of the system for preparing the deuterium depleted water and the deuterium enriched water by separating the natural water is 8 separation columns (No. 1-8), and the separation columns are sequentially connected end to end through pipelines according to the serial number (No. 1 → No. 2 → … → No. 8 → No. 1) to form a closed loop; the system also comprises a raw material water storage tank, a deuterium-enriched water storage tank, a deuterium-depleted water storage tank, a metering pump, a vaporizer, a vacuum pump, and a pipeline and a valve for connecting the devices.
The separation column, the metering pump, the vaporizer and corresponding connecting pipelines and valves are all placed in a sealed electric heating box, and the box body of the electric heating box is a phenolic foam plate; the bottom of the electric heating box is provided with a dry-burning type electric heating rod, and the outside of the box body is provided with a heating temperature controller, so that the temperature in the box body is controlled to be 105-115 ℃, and on one hand, the temperature of water vapor in the system is ensured to be higher than the boiling point and can not be condensed into liquid water; on the other hand, relatively small temperature fluctuations do not result in a significant change in the water absorption capacity of the filler.
The separation column is a stainless steel pipe with the outer diameter of phi 100, the wall thickness of 3mm and the length of 800, and a stainless steel seal head is welded on the end face of the separation column for sealing; the upper end sealing head of the separation column is connected with the outlet of the one-way valve, the lower end sealing head is connected with the inlet end of the one-way valve of the next-stage separation column, and the connection mode is a phi 10 stainless steel cutting sleeve. The packing in the separation column is a 5A molecular sieve with the grain diameter of phi 3-phi 5, the packing amount of a single column is 3.5kg, and the corresponding water vapor adsorption amount is about 500 g.
The metering pump is a miniature diaphragm pump, output flow is regulated in a two-dimensional mode through stroke and frequency, the stroke is used for coarse regulation of the flow, and the frequency is used for fine regulation of the flow. The vaporizer is a phi 10 stainless steel spiral coil, the coil is arranged in a tubular heating furnace, the temperature of the heating furnace is controlled to be more than 200 ℃, liquid water enters the spiral pipe in a high-temperature state, the liquid water is directly changed into steam by heating and vaporization, no liquid water is retained, and the accurate control of the flow of the raw material steam is facilitated. The vacuum pump is a combination of a water ring pump and a rotary vane pump; the front stage is a water ring pump, and the rear stage is a rotary vane pump with a gas ballast valve. The opening pressure difference of a one-way valve (V1-V8) between the separation columns is set to be 0.1MPa, and when the pressure in the columns exceeds a set value, the one-way flow can be carried out towards the separation column at the rear section.
According to the system composition, the method for separating natural water to prepare deuterium-depleted water and deuterium-enriched water by using a simulated moving bed principle comprises the following specific steps:
s1: controlling the internal temperature of the sealed electric heating box to be 105-115 ℃, starting a heating ring to raise the temperature of each separation column to 350 ℃, vacuumizing to remove residual water vapor of the separation columns, and finally enabling the steady-state vacuum degree to be better than 10 Pa; the heating coil was then turned off and the column temperature was reduced to 115 ℃.
S2: extracting natural water in a raw material water storage tank through a miniature metering pump, converting the natural water into water vapor through a vaporizer, and feeding the water vapor into a 1# to 7# separation column; when the pressure in the 7# column reached 0.02MPa, it indicated that the water vapor adsorption was saturated, and the total amount of water vapor adsorption was about 3500 g.
S3: starting a heating ring to raise the temperature of the 1# separation column to 350 ℃, desorbing water vapor in the 1# column, raising the pressure in the column, and when the pressure exceeds the opening pressure of a one-way valve by 0.1MPa, moving the water vapor backwards to enter the 2# column, so that the water vapor in the 2# column enters the 3# column through the one-way valve, and the subsequent separation columns have similar processes, so that all the water vapor in the 1# to 7# separation column finally enters the 2# to 8# separation column to finish the first rearrangement; the concentration of deuterium in water vapor gradually decreases along # 2 → # 8. When the pressure in the 1# separation column does not change significantly, the desorption is finished, and then the vacuum is pumped to remove residual water vapor in the 1# separation column so as to regenerate the column, and meanwhile, the corresponding heater is turned off.
S4: when the temperature of the 1# column is reduced to 115 ℃, the 2# column is started to heat, the water vapor is desorbed and moves backwards under the driving of pressure difference, and the water vapor completely enters the 3# to 8# and 1# separation columns to complete the second rearrangement. After the 2# column desorption is finished, carrying out 2# column regeneration and 3# column desorption in the same manner; the subsequent separation column operation is analogized in turn.
After the 8# separation column is desorbed, the water vapor is rearranged for the 8 th time, and the water vapor is distributed on the 1# to 7# separation columns again, which shows that the system completes one cycle separation; the water vapor forms a significant deuterium concentration gradient, with the highest deuterium concentration at the top of the 1# column at the proximal end and the lowest deuterium concentration at the bottom of the 7# column at the distal end.
S5: extracting products and filling raw materials according to basic experimental data and a material conservation principle: connecting a deuterium-enriched water storage tank pipeline, heating the No. 1 separation column, and discharging deuterium-enriched water from the top of the column, wherein the collection amount of the deuterium-enriched water is about 200g, and the concentration of deuterium is about 270 ppm; connecting a pipeline of a deuterium-depleted water storage tank, heating a No. 7 separation column, and discharging the deuterium-depleted water from the bottom of the column, wherein the collection amount of the deuterium-depleted water is about 300g, and the concentration of deuterium is about 80 ppm.
S6: deuterium content sampling analysis is carried out on water vapor in No. 2-No. 6 separation columns, the No. 5 separation columns with the deuterium content close to that of natural water are injected from the top of No. 5 separation columns, the natural water deuterium content is about 150ppm, and the injection amount is 500 g; on the basis of the method, no obvious influence is formed on the deuterium concentration gradient of the water vapor distribution zone.
By repeating the above steps, deuterium depleted water having a deuterium concentration of about 80ppm and deuterium enriched water having a deuterium concentration of 270ppm can be prepared in a semi-continuous mode.
Example 2: double circulation mode deuterium-depleted water preparation with 30ppm deuterium concentration
The first cycle of separation was performed according to steps S1-S4 of example 1;
the second cycle separation was performed according to the steps S3-S4 of example 1;
then a pipeline of a deuterium-enriched water storage tank is connected, the No. 1 separation column is heated, deuterium-enriched water is discharged from the top of the column, the collection amount of the deuterium-enriched water is about 160g, and the concentration of deuterium is about 410 ppm; connecting a pipeline of a deuterium-depleted water storage tank, heating a No. 7 separation column, and discharging the deuterium-depleted water from the bottom of the column, wherein the collection amount of the deuterium-depleted water is about 340g, and the concentration of deuterium is about 30 ppm.
Deuterium content sampling analysis is carried out on water vapor in No. 2-No. 6 separation columns, and natural water vapor is injected from the top of No. 4 separation columns with the deuterium content close to that of natural water, wherein the injection amount is 500 g.
By repeating the above steps, deuterium depleted water having a deuterium concentration of about 30ppm and deuterium enriched water having a deuterium concentration of 410ppm can be prepared in a semi-continuous mode.
The separation system has the advantages of simple structure, cheap filling materials, convenient control, smaller equipment scale and lower construction cost, can be used for separating natural water in a semi-continuous mode to directly separate deuterium-depleted water and deuterium-enriched water, and has high separation efficiency and good separation effect.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (9)
1. A system for separating natural water to prepare deuterium depleted water and deuterium enriched water is characterized by comprising a sealed electric heating box, a separation component arranged in the electric heating box, a raw material water storage tank (3), a deuterium enriched water storage tank (4) and a deuterium depleted water storage tank (5) which are arranged outside the electric heating box; the separation assembly comprises No. 1-n separation columns (1) which are connected in series to form a closed loop, and adjacent separation columns are connected through a pipeline provided with a one-way valve (11); a raw material water inlet pipe (31) is arranged on the raw material water storage tank (3), the raw material water inlet pipe penetrates through the electric heating box, a metering pump (33) is arranged on the raw material water inlet pipe (31) outside the electric heating box, a vaporizer (34) is arranged on the raw material water inlet pipe in the electric heating box, and the upper ends of the No. 1 to No. n-1 separation columns are respectively connected with a raw material water inlet pipe pipeline through No. 1 to No. n-1 feeding valves (32) corresponding to the separation columns; the deuterium-enriched water storage tank (4) is provided with a deuterium-enriched water pipe (41) which penetrates through the electric heating box, and the upper end of the No. 1 separation column is communicated with the deuterium-enriched water pipe through a deuterium-enriched water valve (42); the deuterium depleted water storage tank (5) is provided with a deuterium depleted water pipe (51), the deuterium depleted water pipe penetrates through the electric heating box, the lower end of the n-number separation column is communicated with the deuterium depleted water pipe through a deuterium depleted water valve (52), and the separation column (1) adopts a molecular sieve as a filler.
2. The system for separating natural water to prepare deuterium depleted water and deuterium enriched water according to claim 1, further comprising a vacuum pump (2) disposed outside the electric heating box, wherein a vacuum pipe (21) is disposed on the vacuum pump and penetrates through the electric heating box, and the lower ends of the No. 1 to No. n separation columns are respectively connected with vacuum pipe pipelines through No. 1 to No. n vacuum valves (22) corresponding to the lower ends of the No. 1 to No. n separation columns.
3. The system for separating natural water to prepare deuterium depleted water and deuterium enriched water according to claim 2, wherein said electric heating box is a phenolic foam board box, and a dry-fire type electric heating rod is arranged at the bottom of the electric heating box, and the temperature in the box is not lower than 100 ℃.
4. The system for separating natural water to prepare deuterium depleted water and deuterium enriched water according to claim 3, wherein the separation column is a stainless steel tube with phi 50-phi 250, a stainless steel end socket is welded on the end face of the separation column, stainless steel corrugated tubes with phi 10-phi 20 are connected, and the corrugated tubes are connected through a clamping sleeve or a welding mode.
5. The system for separating natural water to prepare deuterium depleted water and deuterium enriched water according to any one of claims 2 to 4, wherein the outer wall of the separation column is wrapped by a stainless steel mica thin-wall annular heating ring so that the rated service temperature is not lower than 500 ℃.
6. The system for separating natural water into deuterium depleted water and deuterium enriched water according to claim 5, wherein said metering pump (33) is a diaphragm pump.
7. The system for separating natural water to prepare deuterium depleted water and deuterium enriched water according to claim 6, wherein said vaporizer (34) is a stainless steel spiral coil placed in a heating furnace, liquid water enters the coil at high temperature, and is vaporized by heat to become steam directly, and no liquid water is retained.
8. The system for separating natural water to prepare deuterium depleted water and deuterium enriched water according to claim 6 or 7, wherein said vacuum pump (2) is a combination of water ring pump and rotary vane pump, the former stage is water ring pump and the latter stage is rotary vane pump with ballast valve.
9. The method for preparing deuterium depleted water and deuterium enriched water using the system of claim 8, comprising the steps of:
s1: setting the internal temperature of the electric heating box to be more than 100 ℃, starting a heating ring outside the separation columns to increase the temperature of each separation column to be more than 300 ℃, vacuumizing to remove residual water vapor in the separation columns, and then reducing to 100 ℃;
s2: natural water in a raw material water storage tank is pumped by a metering pump, and then is converted into water vapor by a vaporizer, and then enters a No. 1-n-1 separation column;
s3: starting a heating ring to enable the temperature of the No. 1 separation column to rise to more than 300 ℃, desorbing water vapor in the No. 1 separation column, enabling the pressure in the column to rise, enabling the water vapor to move backwards to enter the No. 2 column when the pressure of the check valve is exceeded, further enabling the water vapor of the No. 2 column to enter the No. 3 column through the check valve, enabling the subsequent separation columns to sequentially perform the process, finally enabling the water vapor in the No. 1-n-1 separation column to completely enter the No. 2-n separation column, finishing the first rearrangement, gradually reducing the concentration of deuterium in the water vapor along No. 2 → n, vacuumizing to remove residual water vapor of the No. 1 column to regenerate the separation column when the pressure in the No. 1 separation column is not obviously changed, and simultaneously closing the No. 1 column heating ring;
s4: when the temperature of the No. 1 column is reduced to 100 ℃, starting the No. 2 column for heating, desorbing water vapor and moving backwards under the driving of pressure difference, wherein the water vapor completely enters the No. 3-n and No. 1 separation columns to finish the second rearrangement; after the desorption of the No. 2 column is finished, the No. 2 column regeneration and the No. 3 column desorption are carried out according to the same mode; the subsequent separation column operation is analogized in turn; after the n separation column is desorbed, the water vapor is rearranged for the n time, and the water vapor is distributed on the 1 to n-1 separation columns again, which indicates that the system completes one cycle separation;
s5: connecting a deuterium-enriched water storage tank pipeline, starting a heating ring to heat the No. 1 separation column, and discharging and collecting deuterium-enriched water from the top of the No. 1 separation column; connecting a pipeline of a deuterium depleted water storage tank, heating the n-1 separation column, and discharging and collecting deuterium depleted water from the bottom of the column; then, raw material water is injected from the middle section of the separation loop, and then the next circulation separation operation can be carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811216421.2A CN109455669B (en) | 2018-10-18 | 2018-10-18 | System and method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811216421.2A CN109455669B (en) | 2018-10-18 | 2018-10-18 | System and method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109455669A CN109455669A (en) | 2019-03-12 |
| CN109455669B true CN109455669B (en) | 2020-05-19 |
Family
ID=65607919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811216421.2A Active CN109455669B (en) | 2018-10-18 | 2018-10-18 | System and method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109455669B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7492553B2 (en) | 2022-06-03 | 2024-05-29 | 大陽日酸株式会社 | Deuterated ammonia production equipment |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111419083B (en) * | 2020-04-03 | 2023-04-07 | 中国工程物理研究院材料研究所 | Integrated miniaturized low-deuterium water dispenser |
| CN114768531B (en) * | 2022-05-31 | 2023-04-07 | 中国工程物理研究院材料研究所 | Hydrogen isotope water separation system and method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1467183C3 (en) * | 1964-06-24 | 1974-06-12 | Friedrich Uhde Gmbh, 4600 Dortmund | Process for the enrichment of deuterium through isotope exchange |
| US4915929A (en) * | 1988-01-25 | 1990-04-10 | Iowa State University Research Foundation, Inc. | Isotopic separation of D2 O from H2 O using ruthenium adsorbent |
| CN105036078B (en) * | 2015-09-07 | 2017-03-22 | 中国工程物理研究院材料研究所 | Deuterium-depleted water preparation system and implementation method thereof |
| CN107098413B (en) * | 2017-05-16 | 2020-05-22 | 中国工程物理研究院材料研究所 | Rectification process system for preparing deuterium-depleted water with various concentrations and implementation method thereof |
| CN107128877B (en) * | 2017-05-18 | 2019-05-03 | 中国工程物理研究院材料研究所 | A kind of liquid-phase catalysis exchange technique prepares the method and device of low deuterium-oxide |
| CN108083229B (en) * | 2017-12-13 | 2020-11-06 | 中国工程物理研究院材料研究所 | System for preparing multi-concentration deuterium-depleted water by liquid-phase catalytic exchange process and implementation method thereof |
-
2018
- 2018-10-18 CN CN201811216421.2A patent/CN109455669B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7492553B2 (en) | 2022-06-03 | 2024-05-29 | 大陽日酸株式会社 | Deuterated ammonia production equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109455669A (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105023621B (en) | The implementation and its nuclear reactor of fast heap-type coupling nuclear reaction | |
| CN109455669B (en) | System and method for preparing deuterium-depleted water and deuterium-enriched water by separating natural water | |
| CN101850215B (en) | Low-temperature displacement chromatography hydrogen isotope separation device and method | |
| CN105600752B (en) | A kind of method of purification and its system for being used for hydrogen in biological fuel gas | |
| CN109289526B (en) | Rotary low-temperature hydrogen isotope separation system and separation method | |
| CN109942005B (en) | Industrial production method of boron-10 isotope | |
| CN106693703B (en) | A kind of displacement chromatography hydrogen isotope separation device | |
| CN106807387B (en) | A kind of bifunctional catalyst and preparation method thereof for absorption enhancement hydrogen production by bio-oil steam reforming | |
| Heung et al. | TCAP hydrogen isotope separation using palladium and inverse columns | |
| RU2328336C2 (en) | Method and device for cleaning and separating concentrate of heavy target components with obtaining target components of concentrate and light elements isotopes | |
| US11389766B2 (en) | System and method for separating xenon-krypton mixed gas by hydrate formation process | |
| Chen et al. | Novel exchanger type vacuum temperature swing adsorption for post-combustion CO2 capture: Process design and plant demonstration | |
| CN204897394U (en) | Low deuterium -oxide preparation system | |
| CN104828778A (en) | Simultaneous upgrading and tritium removal process of heavy water | |
| CN208332856U (en) | Purification device in liquefaction of hydrogen device | |
| CN109872828B (en) | System and method for separating xenon-krypton gas mixture by using hydrate method | |
| CN114768531B (en) | Hydrogen isotope water separation system and method | |
| CN106115700B (en) | Beam tube type water bed moves the compound CO converting means of heat and conversion process | |
| CN104147928A (en) | Rapid removing method for protium in gas-containing tritium hydrogen isotope | |
| CN218280643U (en) | A separator for panaxtriol saponins | |
| CN104128093B (en) | A kind of hydrogen isotope method for gas purification | |
| CN203807154U (en) | System for collecting high-concentration tritium by adopting vapor phase catalysis mode | |
| CN205824602U (en) | A kind of low pressure adsorbent natural gas storage tank | |
| CN208419720U (en) | A kind of chemical industry volumetric heat exchanger | |
| CN108083229B (en) | System for preparing multi-concentration deuterium-depleted water by liquid-phase catalytic exchange process and implementation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |