CN109465034A - It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid - Google Patents
It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid Download PDFInfo
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- CN109465034A CN109465034A CN201811331130.8A CN201811331130A CN109465034A CN 109465034 A CN109465034 A CN 109465034A CN 201811331130 A CN201811331130 A CN 201811331130A CN 109465034 A CN109465034 A CN 109465034A
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- catalyst
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- dissolved oxygen
- eliminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of for eliminating the catalyst of dissolved oxygen in liquid comprising: carrier, the carrier are anion exchange resin, coefficient of uniformity≤1.1 of the anion exchange resin；Active component, the active component are precious metal palladium, and the precious metal palladium is distributed in the carrier with elemental form.Provided by the present invention for eliminating the catalyst of dissolved oxygen in liquid, use environment temperature by 40 DEG C 60 DEG C will be increased in the prior art, thermal stability improves, and total organic carbon release is low, has widened application range, runnability will not change.
Description
Technical field
The present invention relates to a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid.
Background technique
At normal temperatures and pressures, can be dissolved with a certain amount of oxygen in water, dissolved oxygen concentration is generally 8~10 mg/L.In nuclear power
In the various fields such as demineralized water, boiler feedwater and semiconductor ultrapure water of standing, the dissolved oxygen of high concentration can aggravate the corrosion of equipment, from
And shorten the service life of equipment, accident can be caused under serious conditions.Therefore, it is dense that oxygen in water is strictly limited in industrial applicability
Degree, for example nuclear plant desalting water system is no more than 20 μ g/L, even lower than 10 μ g/L；" GB1576-2008 Industrial Boiler water
Matter " in regulation: rated capacity is greater than or equal to the boiler of 10t/h, and deoxygenation is answered in water supply, and oxygen content is less than or equal to 0.05mg/
L。
Traditional dissolved oxygen minimizing technology has thermal de-aeration, deaeration in condenser, Deadsorbing and oxygen removing, chemical deoxidization etc., but no matter
Which kind of method is all had some limitations due to the defect of itself, is not that the water quality that can make that treated changes and (such as contains
Hydrazine and it is toxic；Increase CO2Content and reduce pH value；Increase the drying surplus of water；Or generate ferrous iron), it is exactly to require a high position
Arrange or take up a large area or it is complicated for operation, operating cost is high.It is generally acknowledged that atmospheric-type thermodynamic deoxidizing effect is relatively stable,
On water quality without influence, but still require that high-order arrangement；A large amount of steam are needed, operating cost is higher.The sixties in last century, Bayer Bitterfeld GmbH
It is Lewstit OC-1045 type catalytic resin that company, which develops and produces the trade mark, proposes " catalytic resin deoxidization by adding hydrogen side
Method " --- a kind of reducing agent (such as hydrogen) appropriate is dissolved in water to be processed, then by catalytic resin bed, hydrogen-oxygen is multiple
It closes to realize deoxygenation, especially suitable for the oxygen for going to dissolve in water removal in the production process of ultrapure water.The resin is a kind of ball
The strong basicity gel-type palladium doped polymeric resin of state, using temperature no more than 40 DEG C.
The Lewstit OC-1045 type catalytic resin of German Bayer AG is mixed using anion exchange resin as carrier
Miscellaneous precious metal palladium, palladium are attached on carrier with elemental form.When in use, which is only used for 40 DEG C or less liquid phase environments,
When temperature is greater than 40 DEG C, which may change, and releasing organics and skeleton catabolite are into liquid phase, to liquid
Phase main body pollutes, deoxygenation performance also phase strain differential, causes total content of organic carbon exceeded (being greater than 50ppb), i.e., existing catalysis
Resin thermal stability is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention proposes a kind of for eliminating the catalyst of dissolved oxygen in liquid.
Provided by the present invention for eliminating the catalyst of dissolved oxygen in liquid, comprising:
Carrier, the carrier are anion exchange resin, coefficient of uniformity≤1.1 of the anion exchange resin；
Active component, the active component are precious metal palladium, and the precious metal palladium is distributed in the carrier with elemental form
It is interior.
Preferably, the anion exchange resin is the anion exchange resin that heatproof is greater than 60 DEG C.
Another object of the present invention is to propose a kind of above-mentioned for eliminating the preparation side of the catalyst of dissolved oxygen in liquid
Method includes the following steps:
Using anion exchange resin as carrier；
Using palladium chloride, palladium nitrate or palladium acetate as precursor, it is made into the precursor solution that concentration is 0.1~10g/L；
Successively use 1%~10% sodium hydroxide solution and ultrapure water with 1~50BV/h rate in chromatographic column to described
Carrier is washed；
Carrier after washing is put into stirring container with the precursor solution, impregnates 1~48h, dipping temperature is 0~70
℃；
After dipping, using the above-mentioned mixed liquor of milli-Q water；
After washing, to after washing mixed liquor be added reducing agent, reduction 3~for 24 hours；
Mixed liquor after washing reduction in chromatographic column using ultrapure water and nitrogen mixture；
1%~10% sodium hydroxide solution and ultrapure water is used to carry out in chromatographic column to carrier with 1~50BV/h rate
Washing；
Free water is extracted out using Suction filtration device.
Preferably, the volume ratio of the precursor solution and the carrier is 0.1~10:1.
Preferably, when using milli-Q water after dipping, ultrapure water rate is 1~50BV/h.
Preferably, the reducing agent is hydrazine hydrate, glucose, sodium formate, ascorbic acid, sodium borohydride or formaldehyde.
Preferably, the molar ratio of the reducing agent and the palladium dosage in the precursor is 1~10:1, the reducing agent and institute
The volume ratio for stating carrier is 0.2~2:1.
Preferably, after reduction, when washing the mixed liquor after restoring in chromatographic column using ultrapure water and nitrogen mixture, surpass
Pure water rate is 1~50BV/h, and nitrogen rate is 0.5~8 times of ultrapure water.
Preferably, the anion exchange resin is the anion exchange resin that heatproof is greater than 60 DEG C.
Compared with prior art, the invention has the following advantages:
1, provided by the present invention for eliminate liquid in dissolved oxygen catalyst, will in the prior art use environment temperature by
40 DEG C are increased to 60 DEG C, and thermal stability improves, and total organic carbon release is low, have widened application range, runnability will not change
Become.
2, provided by the present invention for the catalyst of dissolved oxygen in elimination liquid, coefficient of uniformity is no more than 1.1, so that using
The reactor operation pressure drop of the catalyst reduces, and resistance reduces, and reduces energy consumption.
3, provided by the present invention for the catalyst of dissolved oxygen in elimination liquid, catalytic hydrogenation side is passed through using the catalyst
Oxygen in water concentration can be down to 20ppb even 10ppb or less by 8ppm by formula.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below with regard to specific embodiment pair
The present invention is described in further detail.
The a kind of of one embodiment of the invention offer is solid catalyst for eliminating the catalyst of dissolved oxygen in liquid, by
Carrier and active component composition.Carrier is the anion exchange resin that heatproof is greater than 60 DEG C, coefficient of uniformity≤1.1；Active component
For precious metal palladium, it is distributed in carrier with elemental form.In use, being filled in the catalyst except in oxygen reactor, hydrogen with
Liquid to be treated be sufficiently mixed after enter reactor, dissolved hydrogen with dissolved oxygen under the action of catalyst react generation water, finally by
Reactor outlet discharge, whole process do not bring pollutant into, and low energy consumption.
It is above-mentioned for eliminate the catalyst of dissolved oxygen in liquid the preparation method is as follows:
Anion exchange resin using heatproof greater than 60 DEG C is as carrier；Before palladium chloride, palladium nitrate or palladium acetate are used as
Body, wiring solution-forming, concentration are 0.1~10g/L；Precursor solution and carrier dosage relation are 0.1~10:1 (volume ratio).Respectively
It, will after using 1%~10% sodium hydroxide solution and ultrapure water to wash in chromatographic column to carrier with 1~50BV/h rate
Carrier and precursor solution are put into stirring container, impregnate 1~48h, and dipping temperature is 0~70 DEG C；After dipping, using ultrapure water
Washing, ultrapure water rate are 1~50 BV/h；After washing, be added reducing agent, reduction 3~for 24 hours, reducing agent used be hydrazine hydrate,
Glucose, sodium formate, ascorbic acid, sodium borohydride, formaldehyde etc., reducing agent and palladium dosage relation are 1~10:1 (molar ratio), also
Former agent and carrier dosage relation are 0.2~2:1 (volume ratio)；After reduction, chromatographed first using ultrapure water and nitrogen mixture
Washing in column, ultrapure water rate are 1~50BV/h, and nitrogen rate is 0.5~8 times of ultrapure water, then with 1%~10% hydrogen-oxygen
Change sodium solution and ultrapure water washs carrier in chromatographic column with 1~50BV/h rate；Finally, being extracted out using Suction filtration device
Extra free water.
Deoxygenation performance evaluation is carried out using above-mentioned catalyst sample, condition is as follows: catalyst amount 1L, pressure are
1.0MPa, temperature are 60 DEG C, water flow 70BV/h, hydrogen flowing quantity 1.08L/h, and oxygen in water is down to 10ppb by 8ppm,
Total organic carbon is released to 20ppb.
Compared with prior art, the present embodiment has the advantages that
1, provided in this embodiment for eliminating the catalyst of dissolved oxygen in liquid, it will use environment temperature in the prior art
60 DEG C are increased to by 40 DEG C, thermal stability improves, and total organic carbon release is low, has widened application range, runnability will not occur
Change.
2, provided in this embodiment for eliminating the catalyst of dissolved oxygen in liquid, coefficient of uniformity is no more than 1.1, so that adopting
It is reduced with the reactor operation pressure drop of the catalyst, resistance reduces, and reduces energy consumption.
3, provided in this embodiment for eliminating the catalyst of dissolved oxygen in liquid, catalytic hydrogenation is passed through using the catalyst
Oxygen in water concentration can be down to 20ppb even 10ppb or less by 8ppm by mode.
Those skilled in the art can use different methods to achieve the described function each specific application, but
It is that such implementation should not be considered as beyond the scope of the present invention.
Obviously, those skilled in the art can carry out various modification and variations without departing from spirit of the invention to invention
And range.If in this way, these modifications and changes of the present invention belong to the claims in the present invention and its equivalent technologies range it
Interior, then the invention is also intended to include including these modification and variations.
Claims (9)
1. a kind of for eliminating the catalyst of dissolved oxygen in liquid characterized by comprising
Carrier, the carrier are anion exchange resin, coefficient of uniformity≤1.1 of the anion exchange resin；
Active component, the active component are precious metal palladium, and the precious metal palladium is distributed in the carrier with elemental form.
2. as described in claim 1 for eliminating the catalyst of dissolved oxygen in liquid, which is characterized in that the anion exchange
Resin is the anion exchange resin that heatproof is greater than 60 DEG C.
3. a kind of of any of claims 1 or 2 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, feature exists
In including the following steps:
Using anion exchange resin as carrier；
Using palladium chloride, palladium nitrate or palladium acetate as precursor, it is made into the precursor solution that concentration is 0.1~10g/L；
Successively use 1%~10% sodium hydroxide solution and ultrapure water with 1~50BV/h rate in chromatographic column to the carrier
It is washed；
Carrier after washing is put into stirring container with the precursor solution, impregnates 1~48h, dipping temperature is 0~70 DEG C；
After dipping, using the above-mentioned mixed liquor of milli-Q water；
After washing, to after washing mixed liquor be added reducing agent, reduction 3~for 24 hours；
Mixed liquor after washing reduction in chromatographic column using ultrapure water and nitrogen mixture；
1%~10% sodium hydroxide solution and ultrapure water is used to wash in chromatographic column to carrier with 1~50BV/h rate；
Free water is extracted out using Suction filtration device.
4. as claimed in claim 3 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, which is characterized in that described
The volume ratio of precursor solution and the carrier is 0.1~10:1.
5. as claimed in claim 3 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, which is characterized in that dipping
When using milli-Q water afterwards, ultrapure water rate is 1~50BV/h.
6. as claimed in claim 3 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, which is characterized in that described
Reducing agent is hydrazine hydrate, glucose, sodium formate, ascorbic acid, sodium borohydride or formaldehyde.
7. as claimed in claim 6 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, which is characterized in that described
The molar ratio of palladium dosage in reducing agent and the precursor is 1~10:1, and the volume ratio of the reducing agent and the carrier is 0.2
~2:1.
8. as claimed in claim 3 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, which is characterized in that reduction
Afterwards, when washing the mixed liquor after restoring in chromatographic column using ultrapure water and nitrogen mixture, ultrapure water rate is 1~50BV/
H, nitrogen rate are 0.5~8 times of ultrapure water.
9. as claimed in claim 3 for eliminating the preparation method of the catalyst of dissolved oxygen in liquid, which is characterized in that described
Anion exchange resin is the anion exchange resin that heatproof is greater than 60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811331130.8A CN109465034A (en) | 2018-11-09 | 2018-11-09 | It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811331130.8A CN109465034A (en) | 2018-11-09 | 2018-11-09 | It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid |
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| CN109465034A true CN109465034A (en) | 2019-03-15 |
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| CN201811331130.8A Pending CN109465034A (en) | 2018-11-09 | 2018-11-09 | It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113786861A (en) * | 2021-08-06 | 2021-12-14 | 宁波争光树脂有限公司 | Preparation method of palladium-loaded deoxygenation catalytic resin special for nuclear power |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB924298A (en) * | 1959-02-12 | 1963-04-24 | Bayer Ag | A method of removing oxygen dissolved in water by means of anion exchange resins |
| US6589427B2 (en) * | 2001-02-28 | 2003-07-08 | Council Of Scientific & Industrial Research | Process for treatment of mixture of spent wash from distillery and black liquor from pulp and paper industry |
| CN101346364A (en) * | 2005-12-20 | 2009-01-14 | 利安德化学技术有限公司 | Process for oxidizing organic compounds |
| CN101549291A (en) * | 2009-05-08 | 2009-10-07 | 西安凯立化工有限公司 | Catalyst for removing dissolved oxygen in water and preparing method thereof |
| US7851406B2 (en) * | 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 |
| CN104084196A (en) * | 2014-07-04 | 2014-10-08 | 哈尔滨工程大学 | Preparation method of carbonized Pd (palladium)-carrying hollow anion exchange resin microsphere H2O2 (hydrogen peroxide) electroreduction catalyst |
| CN107456997A (en) * | 2017-09-05 | 2017-12-12 | 泉州市科茂利通智能科技有限公司 | A kind of Nanoscale Iron palladium resin for industrial water deoxygenation and preparation method thereof |
| CN108164622A (en) * | 2018-02-28 | 2018-06-15 | 江苏苏青水处理工程集团有限公司 | A kind of preparation method of Thermal Stable Anion Exchange Resin |
-
2018
- 2018-11-09 CN CN201811331130.8A patent/CN109465034A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB924298A (en) * | 1959-02-12 | 1963-04-24 | Bayer Ag | A method of removing oxygen dissolved in water by means of anion exchange resins |
| US6589427B2 (en) * | 2001-02-28 | 2003-07-08 | Council Of Scientific & Industrial Research | Process for treatment of mixture of spent wash from distillery and black liquor from pulp and paper industry |
| CN101346364A (en) * | 2005-12-20 | 2009-01-14 | 利安德化学技术有限公司 | Process for oxidizing organic compounds |
| US7851406B2 (en) * | 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 |
| CN101549291A (en) * | 2009-05-08 | 2009-10-07 | 西安凯立化工有限公司 | Catalyst for removing dissolved oxygen in water and preparing method thereof |
| CN104084196A (en) * | 2014-07-04 | 2014-10-08 | 哈尔滨工程大学 | Preparation method of carbonized Pd (palladium)-carrying hollow anion exchange resin microsphere H2O2 (hydrogen peroxide) electroreduction catalyst |
| CN107456997A (en) * | 2017-09-05 | 2017-12-12 | 泉州市科茂利通智能科技有限公司 | A kind of Nanoscale Iron palladium resin for industrial water deoxygenation and preparation method thereof |
| CN108164622A (en) * | 2018-02-28 | 2018-06-15 | 江苏苏青水处理工程集团有限公司 | A kind of preparation method of Thermal Stable Anion Exchange Resin |
Non-Patent Citations (1)
| Title |
|---|
| 陈志和主编: "《电厂化学设备及系统》", 31 March 2006 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113786861A (en) * | 2021-08-06 | 2021-12-14 | 宁波争光树脂有限公司 | Preparation method of palladium-loaded deoxygenation catalytic resin special for nuclear power |
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