CN101549291B - Catalyst for removing dissolved oxygen in water and preparing method thereof - Google Patents
Catalyst for removing dissolved oxygen in water and preparing method thereof Download PDFInfo
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- CN101549291B CN101549291B CN2009100224302A CN200910022430A CN101549291B CN 101549291 B CN101549291 B CN 101549291B CN 2009100224302 A CN2009100224302 A CN 2009100224302A CN 200910022430 A CN200910022430 A CN 200910022430A CN 101549291 B CN101549291 B CN 101549291B
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- resin
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Abstract
The invention relates to a catalyst for removing dissolved oxygen in water and a preparing method thereof. The catalyst comprises resin as a carrier and active noble metal component palladium that is loaded on the resin, and the weight percentage of palladium is 0.1 to 1 percent. The preparing method of the catalyst is as follows: after certain treatment, resin is added into PdCl2 solution with certain pH value so as to be soaked, then aging and filtering are carried out, after a filter cake is beaten, reduction is executed by using a chemical reduction method, the active component of metal palladium is distributed on the surface of the resin uniformly in the form of highly dispersed nanometer grains, and then filtering and washing are executed until no chloride ion exists, thus obtaining the nanometer Pd/resin catalyst. The catalyst can remove the dissolved oxygen in water effectively and be used for removing oxygen in boiler water, the residual oxygen of the effluent water can be reduced to under 0.01mg/L, and the catalyst has great industrial application potential.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, particularly relate to a kind of Catalysts and its preparation method that is used to remove oxygen in water.
Background technology
Contain a large amount of dissolved oxygens in the water, the existence of a large amount of dissolved oxygens is to the safe operation and the very big harmful effect of production equipment life of equipment, particularly for secondary circuit water, condensed water in some precisions and the key equipment, the requirement oxygen in water must be low, to prevent and to reduce equipment corrosion, guarantee the equipment security of operation.In daily life, the dissolved oxygen in the water causes very big influence to the corrosion and the safe operation meeting of boiler, therefore must remove the oxygen in anhydrating.For this reason, " low-pressure boiler water standard " (GB1576-96) requires evaporation capacity must install the feedwater deaeration device greater than the steam boiler of 6th.
Deoxygenation technology mainly contains thermal de-aeration, deaeration in condenser, Deadsorbing and oxygen removing, chemical method deoxygenation etc., and wherein the chemical method deoxygenation is not owing to need big equipment, power input, and deaerating effect is good and become the emphasis and the focus of domestic and international research.
(1) redoxite deoxidation method.Redoxite is a resinoid that can carry out electron exchange with active material on every side with having, redox reaction takes place.The principle of deoxygenation is the resin with original reduction form, changes the resin of oxidised form into, after resin uses, by reducing agent regeneration, recovers its reducing power.But hydrazine hydrate is adopted in regeneration, and human body is had carcinogenesis.Hydrazine hydrate price height causes the operating cost height in addition.
(2) steel cuttings deoxygenation.Novel TL-A type, steel scrap is cast the irregular sphere of 3mm～5mm by prescription, in jar after the vulcanizing treatment, in water temperature 〉=40 ℃, under the condition of time of contact 〉=2 minute, can reach deaerating effect preferably, and residual oxygen content is 0.05mg/L; But the deoxygenation afterproduct is easy-clear not, and difficult backwash is easily hardened, and changes difficulty.
(3) chemical reagent deoxygenation.Utilize a certain chemical substance that can react with the dissolved oxygen in the water, and with the used up a kind of method of oxygen in water.Oxygen scavenging chemical mainly contains sodium sulfite and hydrazine etc., but this method easily produces the material that some are pernicious to people.
Summary of the invention
Technical problem to be solved by this invention is the shortcoming that exists at prior art, provides that a kind of catalytic activity is good, selectivity is high, can remove the catalyst of oxygen in water effectively.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of catalyst that is used to remove oxygen in water, it is characterized in that, form by resin carrier and the nano active Metal Palladium that is carried on the resin, the weight percentage of Metal Palladium is 0.1-1%, described resin is anion exchange resin, cationic ion-exchange resin or polymeric adsorbent, and resin size is 0.5-3mm.
The present invention also provides a kind of Preparation of catalysts method that is used to remove oxygen in water, it is characterized in that this method may further comprise the steps:
(1) processing of resin carrier: resin joined in the deionized water or in the alkaline aqueous solution soak, spend deionised water after the filtration;
(2) preparation of nanometer Pd/ resin catalyst: the resin after handling in the step (1) is under water, add the palladium bichloride saline solution in the resin aqueous systems, with alkaline aqueous solution regulation system pH is 2-7, at room temperature, stirred dipping 3-12 hour, with 5%NaOH regulation system PH is 8-10, placed 6-12 hour, filter, the resin filter cake is gone in the reactor after adding deionized water, adopts chemical reducing agent to reduce, and the activity component metal palladium is evenly distributed on the resin carrier surface with nano-scale particle, filter then and wash to there not being chlorion, promptly obtain nanometer Pd/ resin catalyst.
After stirring dipping in the above-mentioned steps (2), regulating resin aqueous systems pH with alkaline aqueous solution is 8-10.
Described alkaline aqueous solution is NaOH, Na
2CO
3, KOH or K
2CO
3The aqueous solution, its concentration are 0.1-1mol/L.
The volume ratio of palladium bichloride saline solution and vector resin is 1 described in the above-mentioned steps (2): 1-100: 1.
Chemical reducing agent described in the above-mentioned steps (2) is water-soluble reducing agent HCOONa, HCHO, HCOOH, hydrazine hydrate.
The mass ratio of described chemical reducing agent and Metal Palladium is 1: 1-10: 1.
The present invention compared with prior art has the following advantages: catalyst of the present invention can remove the dissolved oxygen in anhydrating effectively, be used for the boiler feed water deoxygenation, the residual oxygen of its water outlet can drop to below the 0.01ml/L, the index that is better than existing 0.05ml/L, use this catalyst to remove oxygen in water, cost is low, and is pollution-free, and its preparation technology is simple.
Below by embodiment technical scheme of the present invention is described in further detail.
The specific embodiment
Embodiment 1
Take by weighing 10L type resin, resin size is 0.5mm, adds mass concentration and be in 0.1% the NaOH solution to soak 5 hours, filters the back with a large amount of deionized waters washings, reaches 8 until pH, soaks in water stand-by.Add palladium bichloride saline solution (containing palladium 50g) in the resin aqueous systems, regulation system pH is 2, at room temperature, stirring dipping 3 hours, is 8 with 5%NaOH solution regulation system pH value, places 10 hours, filter, filter cake adds in the reactor after adding deionized water, adds the 50ml hydrazine hydrate and reduces, and the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 2
Take by weighing 10L type resin, resin size is 0.5mm, adds mass concentration and be in 1% the NaOH solution to soak 2 hours, filters the back with a large amount of deionized waters washings, reaches 10 until pH, soaks in water stand-by.Add palladium bichloride saline solution (containing palladium 50g) in the resin aqueous systems, regulation system pH is 5, at room temperature, stirred dipping 10 hours, PH is 8 with 5%NaOH solution regulation system, places 6 hours, filter, filter cake adds in the reactor after adding deionized water, adds 50gHCOONa and reduces, and the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 3
Measure 10L type resin, resin size is 1mm, adds in the deionized water to soak 4 hours, spends deionised water number time after the filtration, and is under water stand-by.Add palladium bichloride saline solution (containing palladium 12g) in the resin aqueous systems, regulation system pH is 3, at room temperature stirred dipping 6 hours, with 5%NaOH solution regulation system pH value is 8, placed 12 hours, and filtered, filter cake adds in the reactor after adding deionized water, add 500ml HCHO and reduce, the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 4
Measure 10L type resin, resin size is 1mm, adds in the deionized water to soak 4 hours, spends deionised water number time after the filtration, and is under water stand-by.Add palladium bichloride saline solution (containing palladium 12g) in the resin aqueous systems, regulation system pH is 2, at room temperature stirred dipping 6 hours, with 5%NaOH regulation system pH is 9, placed 12 hours, and filtered, filter cake adds in the reactor after adding deionized water, add 500ml HCHO and reduce, the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 5
Take by weighing 10L type resin, resin size is 0.5mm, adds mass concentration and be in 1% the NaOH solution to soak 2 hours, filters the back with a large amount of deionized waters washings, reaches 8 until pH, soaks in water stand-by.Add palladium bichloride saline solution (containing palladium 50g) in the resin aqueous systems, regulation system pH is 5, at room temperature, stirring dipping 10 hours, is 9 with 5%NaOH regulation system pH, places 6 hours, filter, filter cake adds in the reactor after adding deionized water, adds the 500ml hydrazine hydrate and reduces, and the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 6
Take by weighing 10L type resin, resin size is 0.5mm, adds mass concentration and be in 0.5% the NaOH solution to soak 5 hours, filters the back with a large amount of deionized waters washings, reaches 7.5 until pH, soaks in water stand-by.Add palladium bichloride saline solution (containing palladium 50g) in the resin aqueous systems, regulation system pH is 5, at room temperature, stirred dipping 10 hours, with 5%NaOH regulation system pH is 9, places 6 hours, filters, filter cake adds the reduction of 300ml formic acid after adding deionized water, and the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 7
Take by weighing 10L type resin, resin size is 0.5mm, adds mass concentration and be in 0.5% the NaOH solution to soak 5 hours, filters the back with a large amount of deionized waters washings, reaches 10 until pH, soaks in water stand-by.Add palladium bichloride saline solution (containing palladium 50g) in the resin aqueous systems, regulation system pH is 6, at room temperature, stirred dipping 10 hours, with 5%NaOH regulation system PH is 10, and ageing was left standstill 6 hours, filters, filter cake adds the reduction of 300ml formic acid after adding deionized water, and the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Embodiment 8
Measure 10L type resin, resin size is 3mm, adds mass concentration and be in 0.5% the NaOH solution to soak 5 hours, filters the back with a large amount of deionized waters washings, reaches 7.5 until pH, soaks in water stand-by.Add palladium bichloride saline solution (containing palladium 12g) in the resin aqueous systems, regulation system pH is 5.0, at room temperature, stirred dipping 10 hours, with 5%NaOH regulation system PH is 10, places 6 hours, filters, filter cake adds the reduction of 200ml formic acid after adding deionized water, and the catalyst after the reduction washs to filtrate with deionized water does not have Cl
-1Get final product.
Claims (6)
1. Preparation of catalysts method that is used to remove oxygen in water, catalyst is made up of resin carrier and the nano active Metal Palladium that is carried on the resin, the weight percentage of Metal Palladium is 0.1-1%, described resin is anion exchange resin, cationic ion-exchange resin or polymeric adsorbent, resin size is 0.5-3mm, it is characterized in that the preparation method may further comprise the steps:
(1) processing of resin carrier: resin joined in the deionized water or in the alkaline aqueous solution soak, spend deionised water after the filtration;
(2) preparation of nanometer Pd/ resin catalyst: the resin after handling in the step (1) is under water, add the palladium bichloride saline solution in the resin aqueous systems, with alkaline aqueous solution regulation system pH is 2-7, at room temperature, stirred dipping 3-12 hour, with 5%NaOH regulation system pH, placed 6-12 hour, filter, the resin filter cake is gone in the reactor after adding deionized water, adopts chemical reducing agent to reduce, and the activity component metal palladium is evenly distributed on the resin carrier surface with nano-scale particle, filter then and wash to there not being chlorion, promptly obtain nanometer Pd/ resin catalyst.
2. a kind of Preparation of catalysts method that is used to remove oxygen in water according to claim 1 is characterized in that, behind the stirring dipping, is 8-10 with 5%NaOH regulation system pH in the step (2).
3. a kind of Preparation of catalysts method that is used to remove oxygen in water according to claim 1 and 2 is characterized in that described alkaline aqueous solution is NaOH, Na
2CO
3, KOH or K
2CO
3The aqueous solution, its concentration are 0.1-1mol/L.
4. a kind of Preparation of catalysts method that is used to remove oxygen in water according to claim 1 is characterized in that the volume ratio of palladium bichloride saline solution and vector resin is 1-100 described in the step (2): 1.
5. a kind of Preparation of catalysts method that is used to remove oxygen in water according to claim 1 is characterized in that chemical reducing agent described in the step (2) is water-soluble reducing agent HCOONa, HCHO, HCOOH or hydrazine hydrate.
6. a kind of according to claim 1 or 5 Preparation of catalysts method that is used to remove oxygen in water, the mass ratio that it is characterized in that described chemical reducing agent and Metal Palladium is 1-10: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100224302A CN101549291B (en) | 2009-05-08 | 2009-05-08 | Catalyst for removing dissolved oxygen in water and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100224302A CN101549291B (en) | 2009-05-08 | 2009-05-08 | Catalyst for removing dissolved oxygen in water and preparing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101549291A CN101549291A (en) | 2009-10-07 |
| CN101549291B true CN101549291B (en) | 2011-04-20 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109465034A (en) * | 2018-11-09 | 2019-03-15 | 中国船舶重工集团公司第七八研究所 | It is a kind of for eliminating the catalyst and preparation method thereof of dissolved oxygen in liquid |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100998953A (en) * | 2006-01-09 | 2007-07-18 | 中国石油化工股份有限公司 | Preparation method of Pd/resin catalyst |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100998953A (en) * | 2006-01-09 | 2007-07-18 | 中国石油化工股份有限公司 | Preparation method of Pd/resin catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 云霞等.钯/离子交换树脂催化加氢除氧技术的实验研究.《哈尔滨工业大学学报》.2005,第37卷(第2期),249-251. * |
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Granted publication date: 20110420 Termination date: 20120508 |