CN112309601A - Diluent and preparation and application thereof - Google Patents

Diluent and preparation and application thereof Download PDF

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Publication number
CN112309601A
CN112309601A CN201910681713.1A CN201910681713A CN112309601A CN 112309601 A CN112309601 A CN 112309601A CN 201910681713 A CN201910681713 A CN 201910681713A CN 112309601 A CN112309601 A CN 112309601A
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diluent
catalyst
isoolefin
extraction
reaction
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CN112309601B (en
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唐南方
丛昱
商庆浩
陈帅
吴春田
许国梁
苏哲
何辉
袁洁琼
曹智
王文涛
谢书宝
罗方祥
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Dalian Institute of Chemical Physics of CAS
China Institute of Atomic of Energy
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Dalian Institute of Chemical Physics of CAS
China Institute of Atomic of Energy
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G21F9/125—Processing by absorption; by adsorption; by ion-exchange by solvent extraction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a preparation method of a diluent. The method mainly comprises the following steps: using isoolefine and hydrogen as raw material and using Ni-M/Al2O3As a catalyst, the reaction pressure is 1.0MPa to 3.0MPa, the reaction temperature is 200 ℃ to 300 ℃, and the space velocity is 5h‑1‑15h‑1And the hydrogen-oil ratio is 200:1-500:1, and the isoparaffin is generated by reaction. And then, rectifying the generated dodecane to separate out middle fraction, thus obtaining the target diluent. The method has the advantages of mild operation conditions, simple process, catalyst with catalytic activity equivalent to that of noble metal catalyst and low cost.

Description

Diluent and preparation and application thereof
Technical Field
The invention relates to a preparation method of a diluent, in particular to a preparation method of a diluent required in a Purex process.
Background
Spent fuel reprocessing techniques refer to the chemical separation of uranium and plutonium from fission products from uranium wastes that have been used at 3% to 4%. The recovered uranium and plutonium are recycled in the mixed oxide fuel of the nuclear power plant to produce more energy, so that uranium resources are more fully utilized and the demand for uranium enrichment is reduced. The spent fuel post-processing technology is one of the key technologies for guaranteeing the sustainable development of nuclear energy.
The Purex process is a process widely applied to international spent fuel reprocessing at present, tributyl phosphate (TBP) is adopted as an extracting agent in the process, when the TBP is contacted with a spent fuel nitric acid aqueous solution, the TBP can selectively extract uranium and plutonium, the extraction rate of fission products and impurities thereof is extremely low, and the uranium and the plutonium are separated from the fission products through multi-stage countercurrent extraction. TBP has good chemical stability, high flash point, low volatility and poor water miscibility, can be easily regenerated after spent fuel treatment, is convenient to recycle, and is the most suitable extracting agent at present. However, TBP has a high density and viscosity and is not easily contacted with uranium or plutonium in the aqueous phase, and it needs to be diluted in order to obtain an optimum extraction effect. Currently, the common diluents are n-dodecane and higher kerosene. However, the price is high, and the performance still has room for improvement. Therefore, there is still a need to develop a low cost diluent with equal or higher performance.
Disclosure of Invention
The invention aims to provide a preparation method of a low-cost diluent with performance superior to that of n-dodecane and high-grade kerosene.
Based on the purpose, the invention adopts the technical scheme that:
A) based on the content of isoolefin (by mass percent, the content of C10-C12 isoolefin)>75%, C5-C8 fraction less than 5%, C14-C17 fraction less than 5%, and the balance of C9 and C13) and hydrogen as raw materials, and Ni-M/Al2O3As a catalyst, under the conditions that the reaction pressure is 0.5MPa to 5.0MPa, preferably 1MPa to 3MPa, the reaction temperature is 100 ℃ to 400 ℃, preferably 200 ℃ to 300 ℃, the space velocity is 5h-1-20h-1Preferably 5h-1-15h-1The hydrogen-oil ratio is 100:1-800:1, preferably 200:1-500:1, and saturated chain hydrocarbon is generated through reaction under the condition;
B) and (4) rectifying the generated saturated chain hydrocarbon to separate out middle fraction, thus obtaining the target diluent.
The C12 isoolefin content in the step A) is more than 50%.
The catalyst Ni-M/Al in the step A)2O3Wherein M is one or the combination of more than two of La, Ce, Zr, Ga and other metals, the mass fraction of Ni in the catalyst is 5 wt% -25 wt%, preferably 10 wt% -15 wt%, and the mass fraction of M is 0.5 wt% -5 wt%, preferably 1 wt% -2 wt%; al (Al)2O3Is of a mesoporous structure and has a specific surface area of 150m2/g-250m2Per g (preferably 200 m)2/g-240m2(g) with an average pore diameter of 5nm to 8nm, Ni and La being dispersed in Al on an atomic scale2O3On a carrier.
During the rectification treatment in the step B), the theoretical plate number of the rectification column is 100-: 80-140 ℃ (preferably 90-120 ℃), and the kettle pressure is as follows: 0.1kPa to 1kPa (preferably 0.2kPa to 0.6kPa), and fractions with overhead vapor temperatures of 50 ℃ to 75 ℃ (preferably 55 ℃ to 70 ℃) are collected at a reflux ratio of: 10-20 (preferably 10-15).
The diluent prepared by the method is used for a spent fuel extractant, and can selectively extract and separate uranium and plutonium when being contacted with a nitric acid aqueous solution with a spent fuel molar concentration of 3.0mol/L-4.0 mol/L.
The concentration of metal ions in the spent fuel is 0.4mol/L-0.7mol/L.
The invention provides a preparation method of a diluent with high performance and low cost aiming at the problems of the existing diluent. The method has the advantages of mild operation conditions, simple process, catalyst with catalytic activity equivalent to that of noble metal catalyst and low cost.
Detailed Description
To further illustrate the present invention, the following examples are set forth without limiting the scope of the invention as defined by the various appended claims.
Example 1
Preparation of the catalyst:
preparing Ni (NO) according to the final content mass percentages of Ni and La of 10 percent and 2 percent3)2And La (NO)3)3Adding the precursor solution (Ni molar concentration is 2.1mol/L, La molar concentration is 0.18mol/L) into the required mesoporous alumina (specific surface area is 210 m)2(g, average pore diameter is 7nm), stirring uniformly, aging at 60 deg.C for 24h, drying the obtained solid in 120 deg.C oven overnight, and roasting at 450 deg.C for 4h to obtain Ni-La/Al2O3Catalyst (electron microscope results show that Ni and La are dispersed in Al in monoatomic scale2O3Above).
Hydrogenation reaction of raw materials:
taking tetrapropylene (by mass percentage, the content of C10-C12 isoolefin is 76.8%, wherein the content of C12 is 43% of the mass of the tetrapropylene, the content of C5-C8 fraction is 2.1%, the content of C14-C17 fraction is 1.5%, and the balance is C9 and C13) as raw materials, reacting at the reaction temperature: 250 ℃ and reaction pressure: 2MPa, volume space velocity: 10h-1Hydrogen-oil ratio: the hydrogenation reaction is carried out under the reaction condition of 300: 1. The conversion rate of the tetrapropylene hydrogenation product is more than 99.5 percent by using a fluorescence indicator adsorption method.
And (3) rectifying a hydrogenation product:
the theoretical plate number of the rectifying tower is 200, and the temperature of the kettle in the rectifying tower is as follows: 100-125 ℃ and the kettle pressure is as follows: 0.5kPa, collecting the fraction with the overhead vapor temperature of 55-68 ℃, and the reflux ratio is as follows: 15, rectifying the tetrapropylene hydrogenation product under the rectification condition, wherein the cut product is the target diluent (according to the mass percentage content, the content of C10-C12 isoparaffin is 95.6 percent, wherein the content of C12 is 54 percent of the mass of the diluent, the fraction below C8 is 0.4 percent, the fraction above C14 is 0.7 percent, and the rest is C9 and C13 fractions).
Extraction experimental testing of diluents:
1. phase separation time: preparing 30 percent TBP-diluent solution according to the volume ratio, and respectively mixing with 1mol/L HNO3Or the 1mol/L NaOH solution is oscillated in equal volume and fully mixed, then the phase separation time is recorded by standing, and the phase separation time of the two systems is the same and is 0.9 min.
Preparing a 30 percent TBP-n-dodecane solution and 1mol/L HNO respectively according to the volume ratio3Oscillating the solution in equal volume, fully mixing, standing and recording the phase separation time, wherein the phase separation time of the two systems is the same and is 1.5 min; the phase separation time of the target diluent is 0.9min better than 1.5min for n-dodecane.
2. And (3) testing the extraction performance: preparing 30 percent TBP-diluent solution according to the volume ratio, and mixing with 3.5mol/L HNO3The dissolved metal ion solutions with a molar concentration of 0.55mol/L Pu (IV) were mixed well in a volume ratio of 1:1, and the saturated extraction capacity of the metal in a 30% TBP-diluent solution was determined. The extraction saturation capacity of 30 percent TBP-target diluent is 90g/L and the extraction saturation capacity of 30 percent TBP-n-dodecane is 58 g/L.
Example 2
The target diluent obtained in the same manner as described in example 1 except that the reaction temperature in the raw material hydrogenation step was changed to 200 ℃ was subjected to the extraction test (using 1mol/L HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 87g/L during the extraction test.
Example 3
Except in the feed hydrogenation stepThe target diluent obtained in the same manner as described in example 1 except that the temperature was changed to 300 ℃ was subjected to the extraction test (using 1mol/L HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 104g/L during the extraction test.
Example 4
The target diluent obtained in the same manner as described in example 1 except that the reaction pressure in the raw material hydrogenation step was changed to 1MPa, and the extraction experiment test (using 1mol/L HNO) was carried out under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 70g/L during the extraction test.
Example 5
The target diluent obtained in the same manner as described in example 1 except that the reaction pressure in the raw material hydrogenation step was changed to 3MPa, and the extraction experiment test (using 1mol/L HNO) was carried out under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 104g/L during the extraction test.
Example 6
Except that the hollow speed in the step of the hydrogenation reaction of the raw material is changed into 5h-1In addition, the target diluent obtained in the same manner as described in example 1 was subjected to an extraction test (using 1mol/L of HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 108g/L during the extraction test.
Example 7
Except that the hollow speed in the step of the hydrogenation reaction of the raw material is changed into 7.5h-1In addition, the target diluent obtained in the same manner as described in example 1 was subjected to an extraction test (using 1mol/L of HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 104g/L during the extraction test.
Example 8
Except that the hollow speed in the raw material hydrogenation reaction step is changed into 12h-1In addition, the target diluent obtained in the same manner as described in example 1 was subjected to an extraction test (using 1mol/L of HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 93g/L during the extraction test.
Example 9
Except that the space velocity in the step of hydrogenation reaction of raw materials is changed to 15h-1In addition, the target diluent obtained in the same manner as described in example 1 was subjected to an extraction test (using 1mol/L of HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, and 30% TBP-target diluent extraction saturation capacity was 78g/L during the extraction test.
Example 10
Except that the hydrogen-to-oil ratio in the feed hydrogenation step was changed to 200:1 in addition, the target diluent obtained in the same manner as described in example 1 was subjected to the extraction test (using 1mol/L HNO) under the conditions of example 13Phase separation time) was determined, phase separation time was 0.9min better than dodecane, 30% TBP-target diluent extraction saturation capacity was 90g/L during the extraction test.
Example 11
Except that the hydrogen-to-oil ratio in the feed hydrogenation step was changed to 400: 1 in addition, the target diluent obtained in the same manner as described in example 1 was subjected to the extraction test (using 1mol/L HNO) under the conditions of example 13Phase separation time) is determined, in the extraction test process, the phase separation time is better than dodecane at 0.9min, and the extraction saturation capacity of 30% TBP-target diluent is 90 g/L.
Example 12
Except that the hydrogen-oil ratio in the step of hydrogenation reaction of the raw material was changed to 500:1 in addition, the target diluent obtained in the same manner as described in example 1 was subjected to the extraction test (using 1mol/L HNO) under the conditions of example 13Determination of phase separation time) In the extraction test process, the phase separation time is 0.9min and is better than that of dodecane, and the extraction saturation capacity of 30 percent TBP-target diluent is 90 g/L.

Claims (8)

1. A preparation method of a diluent mainly comprises the following steps:
A) using C10-C12 isoolefin and hydrogen as raw material, and Ni-M/Al2O3As a catalyst, under the conditions of reaction pressure of 0.5MPa-5.0MPa, preferably 1-3MPa, reaction temperature of 100-400 ℃, preferably 200-300 ℃ and space velocity of 5h-1-20h-1Preferably 5h-1-15h-1The hydrogen-oil ratio is 100:1-800:1, preferably 200:1-500:1, and saturated chain hydrocarbon is generated through reaction under the condition; m is one or the combination of more than two of La, Ce, Zr, Ga and other metals;
B) and (4) rectifying the generated saturated chain hydrocarbon to separate out middle fraction, thus obtaining the target diluent.
2. The method of claim 1, wherein: the composition of the isomeric olefin containing carbon number C10-C12 comprises the following components in percentage by mass, wherein the content of the isomeric olefin containing carbon number C10-C12 is more than 75%, the content of the isomeric olefin containing carbon number C5-C8 is less than 5%, the content of the isomeric olefin containing carbon number C14-C17 is less than 5%, and the balance is C9 and C13.
3. The method of claim 2, wherein: the C12 isoolefin in the isoolefin containing C10-C12 accounts for more than 40% of the mass of the isoolefin raw material containing C10-C12.
4. The method of claim 1, wherein: the catalyst Ni-M/Al2O3Wherein M is one or the combination of more than two of La, Ce, Zr, Ga and other metals, the mass fraction of Ni in the catalyst is 5 wt% -25 wt%, preferably 10 wt% -15 wt%, and the mass fraction of M is 0.5 wt% -5 wt%, preferably 1 wt% -2 wt%; al (Al)2O3Is of a mesoporous structure and has a specific surface area of 150m2/g-250m2Per g (preferably 200 m)2/g-240m2(g) with an average pore diameter of 5nm to 8nm, Ni and La being dispersed in Al on an atomic scale2O3On a carrier.
5. The method of claim 1, wherein: during the rectification treatment, the theoretical plate number of the rectification tower is 100-: 80-140 ℃ (preferably 90-120 ℃), and the kettle pressure is as follows: 0.1kPa to 1kPa (preferably 0.2kPa to 0.6kPa), and fractions with overhead vapor temperatures of 50 ℃ to 75 ℃ (preferably 55 ℃ to 70 ℃) are collected at a reflux ratio of: 10-20 (preferably 10-15).
6. A diluent prepared by the method of any one of claims 1 to 5.
7. Use of the diluent of claim 6, wherein: the extraction agent for the spent fuel can selectively extract and separate uranium and plutonium when being contacted with a nitric acid aqueous solution with the molar concentration of the spent fuel of 3.0mol/L-4.0 mol/L.
8. Use of a diluent according to claim 7, wherein: the concentration of metal ions in the spent fuel is 0.4mol/L-0.7mol/L.
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