CN106552596A - A kind of de- iodine resin adsorbent and its preparation method and application - Google Patents
A kind of de- iodine resin adsorbent and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of de- iodine resin adsorbent, which comprises the steps：1) cation exchange resin is carried out into vacuum pre-treatment；2) prepare impregnation liquid：Aqueous solution of the impregnation liquid for soluble silver salt, wherein concentration of silver ions are 0.001 1mol/L, adjust pH and are less than 7 to pH value；3) by Jing step 1) process after cation exchange resin and by step 2) obtained in impregnation liquid mixing after impregnated under vacuum；4) cation exchange resin after terminate dipping is separated with impregnation liquid, and is dried, and obtains de- iodine resin adsorbent.The invention further relates to de- iodine resin adsorbent obtained by this method and its application.
Description
Technical field
The present invention relates to a kind of preparation method, more particularly to a kind of preparation method of adsorbent.The invention further relates to
Adsorbent obtained by this method and its application.
Background technology
Acetic acid is a kind of important basic organic chemical industry raw material, be widely used in chemical industry, pesticide, medicine, national defence,
The industries such as electronics.Methyl alcohol carbonyl synthetic method is the widest method used in process of acetic acid for preparing.Monsanto is public
Taking charge of and rhodium series catalysts low pressure carbonylation production technology being have developed in 20 century 70s, iodomethane is used as auxiliary agent.
British Petroleum Company (BP) and Celanese companies are optimized to the technique, are developed with metal iridium respectively
As the AO Plus techniques of the Cativa techniques and low water content of major catalyst, increase substantially acetic acid production capacity.
Although the major catalyst of two kinds of techniques is different, while all auxiliary agent can be made using iodomethane, especially AO Plus
The lithium iodide of high concentration is the use of in technique more.Therefore inevitably contain ioda matter in acetate products.And
When using acetic acid as raw material production downstream product, iodide often result in many catalyst poisoning inactivations.Such as with
When acetic acid and ethylene synthase vinyl acetate, palladium used, Au catalyst are just very sensitive to iodide.Therefore must
A kind of economically viable method must be found to remove the ioda matter in acetic acid.
Ioda matter generally comprises organic iodine and iodide ion with iodomethane as representative.Iodomethane is differed with acetic acid boiling point
It is larger, therefore be easy to be removed by rectification in follow-up separating technology, but the removing of iodide ion is more
It is difficult.The content of ioda matter can only be controlled in ppm levels using traditional rectificating method.Therefore Monsanto
Company has invented two-tower rectification method in patent US3772156, and potassium acetate or hydroxide are added in distillation process
The aqueous solution and hypophosphorous acid of potassium, is allowed to be removed with the iodide ion reaction in acetic acid.
The another kind of method of acetic acid refining is absorption method, is made containing micro (content<1ppm) the acetic acid stream of ioda matter
Jing deiodination adsorbents, so as to highly purified acetic acid is obtained.Sorbent material have ion exchange resin, molecular sieve,
Macromolecule carbon bead etc., these materials Jing different conditions process the metal such as silver, hydrargyrum, palladium on back loading, you can use
Ioda matter in removing acetic acid.
Zeolite molecular sieve is due to big specific surface area, uniform regular pore structure and excellent ion exchangeable
Can, it is used for the research of deiodination adsorbent.Patent CN1709565 is boiled with Hydrogen foresite and Hydrogen ZSM-5
Stone mixing adding additives molding, carries silver again Jing after intensive treatment, and high-strength composite deiodination adsorbent, diameter is obtained
Up to 40 newton/grain, silver carrying amount can reach 10% to 1 millimeter of adsorbent bead intensity.Patent CN101811023
Binding agent molding, hydro-thermal reinforcing will be used after aperture with different structure, hollow and punching zeolite molecular sieve mixing
As carrier after process, it is obtained and carries silver-colored adsorbent, silver carrying amount only reaches 10-15%.
Patent CN86101411 proposes that using the strongly acidic cation-exchange with large network structure which is lived
Property position have 25-75% for silver or hydrargyrum type, using temperature be 18-50 DEG C, but its silver ion be very easy to be lost in,
To be stopped with activated carbon after exchange column using during from above and come off what is fallen with the exchanged resin of silver
Silver.Patent CN1211471 proposes to use gel resin load silver, palladium or hydrargyrum as adsorbent, although patent refers to
Go out to be effectively improved the absorption property of resin, but gel using the shrink form loaded metal ion of gel resin
The swelling problem of resin still seriously limits its commercial Application.
Silver-colored adsorbent is carried for the removing of ioda matter in acetic acid has a preferable effect, but its suction to ioda matter
Attached capacity is limited by silver carrying amount, and silver carrying amount is higher, and the effect for removing ioda matter is better.Simultaneously because load
Silver ion easily by other cation replacements in solution and leach, may need to increase after silver-colored adsorbent bed is carried
One non-adsorbent bed for carrying silver, for adsorbing the silver ion leached by acetic acid to prevent from polluting acetic acid.Therefore, originally
Need a kind of method that processability preferably carries silver-colored adsorbent badly in field.
The content of the invention
In order to solve the problems, such as that silver carrying amount present in above-mentioned prior art is low, silver ion is easy to run off, the present invention is carried
A kind of preparation method of brand-new de- iodine resin adsorbent has been supplied, specifically with cation exchange resin as carrier,
By vacuum impregnation technology load silver ion, deiodination adsorbent is obtained.Inventors hereof have unexpectedly found that,
De- iodine resin adsorbent obtained by this method effectively can remove micro in acetic acid under conditions of high liquid speed
(such as content<Iodide ion 1ppm), overcomes that iodine capacity in existing de- iodine method is low, silver ion is easy to fall off
Problem.
It is an advantage of the invention to provide a kind of preparation method of de- iodine resin adsorbent, which includes as follows
Step：
1) cation exchange resin is carried out into vacuum pre-treatment；
2) impregnation liquid, aqueous solution of the impregnation liquid for soluble silver salt are prepared, wherein concentration of silver ions is
0.01-1mol/L, more preferably preferred 0.02-0.2mol/L, 0.05-0.1mol/L, adjust pH and are less than 7 to pH value,
It is preferred that it is 5-6.9 to adjust pH to pH value；
3) by Jing step 1) process after cation exchange resin and by step 2) obtained in impregnation liquid mixing after
Impregnated under vacuum；
4) cation exchange resin after terminate dipping is separated with impregnation liquid, and is dried, and obtains de- iodine
Resin sorbent.
The present invention some preferred embodiment in, above-mentioned steps 1)-step 4) can be feasible in logic
Random order carry out, such as step 1) can be prior to step 2) carry out, or step 1) step 2 can be later than)
Carry out, or step 1) and step 2) can carry out simultaneously.In an especially preferred reality of the present invention
Apply in mode, by step 1) to step 4) order carry out successively.
Using micro (such as content carried in silver-colored adsorbent removing acetic acid<1ppm) iodide ion, its iodine capacity are complete
All dependent on the silver content of supported on carriers, silver load capacity is higher, and the iodide ion of absorption is more.But existing suction
The attached dose of infusion process load silver for all using routine, in dipping process, as silver ion is diffused into carrier from solution
The speed on surface will far above being diffused into inside the hole of carrier from carrier surface, therefore, silver ion is more loaded
In carrier surface, and the aperture of clogging carrier.Cause the loss of active sites in hole, so as to reduce silver ion
Payload amount.Simultaneously conventional impregnation methods are obtained carries silver-colored adsorbent, the active force phase of silver ion and carrier
To weaker, silver ion is easy to run off in use to make adsorbent, has both reduced the de- iodine performance of adsorbent, together
When the silver ion that comes off easily remain in acetic acid, reduce product quality.And the present inventor exceeds meaning
Material ground finds that using iodine resin adsorbent is taken off obtained in said method, silver ion load capacity is high, and silver ion is being carried
Body upward stability is strong, and when making acetic acid and passing through the adsorbent with high liquid speed, iodide ion is removed, and life-time service is not
It was found that iodide ion content is raised in product, in adsorbent, silver ion content is not reduced.
The preparation method of the de- iodine resin adsorbent of the present invention is prepared using rotatory vacuum infusion process, and first carrier is entered
Row vacuum pre-treatment, adds impregnation liquid and is impregnated, and after gained sample drying, obtains deiodination adsorbent.
The present invention one preferred embodiment in, step 1) described in cation exchange resin be macropore
Cation exchange resin and/or gel-network precipitation method, preferably large hole cation exchanger resin.Macropore
Cation exchange resin has spongiform skeleton, not only internal to have a substantial amounts of micropore, and also big net hole with
Micropore is simultaneously deposited, and its quantity and size can be controlled.And large hole cation exchanger resin heat resisting and pressure resisting, stability
It is high.
The present invention one preferred embodiment in, step 1) described in vacuum pre-treatment in rotary evaporation
Carry out in instrument, treatment conditions are：Vacuum<0.001MPa, temperature are 50-100 DEG C, and process time is 1-5h；
Then it is down to 20-50 DEG C, is preferably dropped to room temperature.
The present invention some preferred embodiment in, the vacuum treated vacuum can be
<0.0005MPa、<0.0001MPa、<0.00008MPa or<0.00005MPa.In some of the invention
In preferred embodiment, the vacuum treated temperature can for 60-100 DEG C, 60-80 DEG C, 70-100 DEG C,
70-80 DEG C etc..The present invention some preferred embodiment in, the vacuum treated process time can be with
For 1-4h, 2-5h, 2-4h, 1-3h, 3-5h or 3-4h etc..
One of the present invention preferred embodiment in, step 2) described in the aqueous solution of soluble silver salt be
The aqueous solution of silver nitrate and/or silver acetate, and using nitric acid and/or acetic acid adjusting pH.
One of the present invention preferred embodiment in, step 3) immersion condition of the dipping is：Vacuum
Degree<0.001MPa, temperature are 20-100 DEG C, are preferably 40-80 DEG C, and dip time is 4-10h, is preferably 4-6h,
Rotary speed>100r/h.
The present invention some preferred embodiment in, the vacuum of the dipping can be<0.0005MPa、
<0.0001MPa、<0.00008MPa or<0.00005MPa.In some of the invention preferred embodiment
In, the temperature of the dipping can for 20-80 DEG C, 20-70 DEG C, 20-60 DEG C, 30-100 DEG C, 30-80 DEG C,
30-50 DEG C, 40-80 DEG C, 50-80 DEG C, 60-80 DEG C, 50-70 DEG C, 60-80 DEG C etc..The present invention's
Some preferred embodiment in, the process time of the dipping can be 4-8h, 4-5h, 5-10h, 5-8h or
5-6h etc..The present invention some preferred embodiment in, the rotary speed of the dipping can be with
For>150r/h、>180r/h、>200r/h、>300r/h or>500r/h etc..
The present invention one preferred embodiment in, step 4) described in be separated into be separated by filtration and/or from
The heart is separated.
The present invention one preferred embodiment in, step 4) described in drying be at 80-150 DEG C,
It is preferred that 5-36h is dried at 105-115 DEG C, preferred 11-13h.
The present invention more one preferred embodiment in, step 4) described in be separated into be separated by filtration and/
Or centrifugation, and step 4) described in drying be at 80-150 DEG C, preferably at 105-115 DEG C do
Dry 5-36h, preferred 11-13h.
The present invention one preferred embodiment in, in step 1) described in pretreatment and step 3) institute
During the dipping stated, keep vacuum to be less than 0.0001MPa, and step 1) in preprocessing process
Vacuum is not less than step 3) in dipping process vacuum.
One of the present invention preferred embodiment in, step 1) described in the temperature of vacuum pre-treatment be
40-80 DEG C, preferably not less than step 3) dipping dipping temperature.
The present invention a more preferred embodiment in, in step 1) described in pretreatment and step 3)
During described dipping, keep vacuum be less than 0.0001MPa, and step 1) in preprocessing process
Vacuum be not less than step 3) in dipping process vacuum,
Also, step 1) described in the temperature of vacuum pre-treatment be 40-80 DEG C, preferably not less than step 3) institute
State the dipping temperature of dipping.
It is a further object of the invention to provide iodine resin adsorbent is taken off according to obtained in said method.
It is still another object of the present invention to provide iodine resin adsorbent is taken off according to obtained in above-mentioned method de-
Application in terms of except iodine, preferably removes content in organic acid, preferred acetic acid<Application in terms of the iodine of 1ppm,
More preferably content is removed in oxo synthesis are obtained acetic acid<Application in terms of the iodine of 1ppm.
One of the present invention preferred embodiment in, by containing the organic acid of iodide ion, preferred acetic acid with
The flow velocity of 1-30BV/h, preferred 5-15BV/h, passes through the de- iodine at 20-80 DEG C, preferably at 40-60 DEG C
Resin sorbent.In the present invention, BV represents a capacity (bed volume).
The present invention one preferred embodiment in, by obtained in said method take off iodine resin adsorbent be placed in
In fixed bed and/or storage tank, then by containing the organic acid of iodide ion, preferred acetic acid with 1-30BV/h, preferably
The flow velocity of 5-15BV/h, passes through the de- iodine resin adsorbent at 20-80 DEG C, preferably at 40-60 DEG C.
Usually ensure de- iodine effect, flow rate of liquid is unsuitable too high during operation, enables organic acid, preferred acetic acid
It is time of contact longer with de- iodine resin adsorbent.But low flow velocity makes the organic acid of process, preferred vinegar in the unit interval
The amount of liquid of acid is reduced, and production efficiency is reduced.In the present invention, as the adsorbent silver ion dispersion that uses is high,
Load capacity is big, it is ensured that still have good de- iodine effect under the conditions of higher liquid speed.The flow velocity of acetic acid
Can be 1-30BV/h, preferred 5-15BV/h.
De- iodine operation can be carried out in wider temperature range, from room temperature to the boiling point less than solution.Although
Under room temperature, the de- iodine preparation can be used, but it is proposed that operated under conditions of hot slightly, take off iodine
Effect is more preferable.Therefore operation temperature is preferred 40-60 DEG C.
The beneficial effects of the present invention is：Under conditions of condition of high vacuum degree, using vacuum-impregnated method by silver from
Son is supported on cation exchange resin, and silver ion is distributed on carrier more uniformly, and silver ion not only can be born
Be loaded in carrier surface, at the same can enter resin hole in, the active sites being carried in hole, substantially increase silver from
The load capacity of son.Condition of high vacuum degree makes silver ion in loading process strengthen with the effect of active sites, with reference to even closer,
Stability of the silver ion on carrier is improve, the losing issue of silver ion is improved.
Specific embodiment
With reference to non-limiting specific embodiment, the invention will be further described, but the protection model of the present invention
Enclose and be not limited to following embodiments.
In the following example, agents useful for same is the conventional commercial reagent in this area, and resin used is commercially available D001
Large hole cation exchanger resin, Rotary Evaporators are 4003 type Rotary Evaporators of commercially available heidolph.
Embodiment 1
The preparation of silver resin adsorbent
20g large hole cation exchanger resins are taken, are put in the evaporative flask of Rotary Evaporators, open vacuum equipment,
100pa is evacuated down to, 80 DEG C are heated to, vacuum state 2h is kept, to discharge the air in molecular sieve pore passage,
Then 30 DEG C are down to.Take 5.112g silver nitrate and be configured to 50ml solution, pH value of solution is adjusted using 2M nitric acid
It is worth for 5, then the solution is slowly added in evaporative flask.Vacuum equipment is opened, 100Pa is evacuated down to,
Continue Stirring, rotating speed is 150rpm, keep solution uniform with mixed with resin, under room temperature, impregnate 8h.Will
Resin takes out, and reduce pressure sucking filtration, after deionized water wash, is dried 13h in 115 DEG C, obtains silver resin absorption
Agent.
De- iodine experiment
Above-mentioned silver resin adsorbent 20mL is taken, is placed in resin bed.Resin bed is heated to into 40 DEG C, containing iodine
The acetum of ion 5ppm passes through adsorbent with 5BV/h.After experiment carries out 24h, iodine in analysis effluent
The content of ion is 0.8ppb, and silver ion do not detect.
Embodiment 2
Take 20g gel-network precipitation methods to be put in the evaporative flask of Rotary Evaporators, open vacuum equipment,
50pa is evacuated down to, 50 DEG C are heated, vacuum state 2h is kept, to discharge the air in resin duct.Take 5.008g
Silver acetate is configured to 100ml solution, and it is 6.8 to adjust solution ph using glacial acetic acid, then will be the solution slow
It is added in evaporative flask.Vacuum equipment is opened, 50Pa is evacuated down to, continues Stirring, rotating speed is 200rpm,
Keep solution uniform with mixed with resin.Rotary Evaporators are heated to into 40 DEG C, 4h is impregnated.To take out,
Decompression sucking filtration, after deionized water wash, is dried 11h in 105 DEG C, obtains silver resin adsorbent.
De- iodine experiment
Above-mentioned load silver adsorbent 20mL is taken, is placed in resin bed.Resin bed is heated to into 60 DEG C, containing iodide ion
The acetum of 1ppm passes through adsorbent with 15BV/h.After experiment carries out 24h, iodide ion in analysis effluent
Content be 0.7ppb, silver ion do not detect.
Embodiment 3
Take 20g large hole cation exchanger resins to be put in the evaporative flask of Rotary Evaporators, open vacuum equipment, take out
Vacuum heats 80 DEG C to 50pa, keeps vacuum state 4h, to discharge the air in resin duct, then drops
To room temperature.Taking 7.015g silver nitrate and being configured to 50ml solution, it is 6 solution ph to be adjusted using 2M nitric acid,
Then the solution is slowly added in evaporative flask.Vacuum equipment is opened, 50Pa is evacuated down to, persistently rotation is stirred
Mix, rotating speed is 200rpm, keep solution uniform with mixed with resin.Rotary Evaporators are heated to into 70V, are soaked
Stain 6h.Resin is taken out, reduce pressure sucking filtration, after deionized water wash, 12h is dried in 110 DEG C, obtain carrying silver
Resin sorbent.
De- iodine experiment
Above-mentioned load silver adsorbent 20mL is taken, is placed in resin bed.Resin bed is heated to into 40 DEG C, containing iodide ion
The acetum of 1ppm passes through adsorbent with 15BV/h.After experiment carries out 24h, iodide ion in analysis effluent
Content be 0.8ppb, silver ion do not detect.
Embodiment 4
Take 20g large hole cation exchanger resins to be put in the evaporative flask of Rotary Evaporators, open vacuum equipment, take out
Vacuum heats 80 DEG C to 100pa, keeps vacuum state 4h, to discharge the air in resin duct, then drops
To room temperature.Taking 7.015g silver nitrate and being configured to 50ml solution, it is 6 solution ph to be adjusted using 2M nitric acid,
Then the solution is slowly added in evaporative flask.Vacuum equipment is opened, 50Pa is evacuated down to, persistently rotation is stirred
Mix, rotating speed is 200rpm, keep solution uniform with mixed with resin.Rotary Evaporators are heated to into 70 DEG C, are soaked
Stain 6h.Resin is taken out, reduce pressure sucking filtration, after deionized water wash, 12h is dried in 110 DEG C, obtain carrying silver
Resin sorbent.
De- iodine experiment
Above-mentioned load silver adsorbent 20mL is taken, is placed in resin bed.Resin bed is heated to into 40 DEG C, containing iodide ion
The acetum of 1ppm passes through adsorbent with 15BV/h.After experiment carries out 24h, iodide ion in analysis effluent
Content be 0.5ppb, silver ion do not detect.
Comparative example 1
Using conventional impregnation, deiodination adsorbent is prepared according to the condition of embodiment 3.
Take 20g large hole cation exchanger resins to be put in beaker.Take 7.015g silver nitrate and be configured to 50ml solution,
It is 6 that solution ph is adjusted using 2M nitric acid, and then the solution is slowly added in beaker.Using electronic or
Magnetic force Stirring, keeps solution uniform with mixed with resin.Solution is heated to into 70 DEG C, 6h is impregnated.Will tree
Fat takes out, and reduce pressure sucking filtration, after deionized water wash, is dried 12h in 110 DEG C, obtains resin sorbent.
De- iodine experiment
Above-mentioned load silver adsorbent 20mL is taken, is placed in resin bed.Resin bed is heated to into 40 DEG C, containing iodide ion
The acetum of 1ppm passes through adsorbent with 15BV/h.After experiment carries out 24h, iodide ion in analysis effluent
Content be 1.5ppb, silver ion 0.8ppb.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in which is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of preparation method of de- iodine resin adsorbent, which comprises the steps：
1) cation exchange resin is carried out into vacuum pre-treatment；
2) impregnation liquid, aqueous solution of the impregnation liquid for soluble silver salt are prepared, wherein concentration of silver ions is
0.01-1mol/L, more preferably preferred 0.02-0.2mol/L, 0.05-0.1mol/L, adjust pH and are less than 7 to pH value,
It is preferred that it is 5-6.9 to adjust pH to pH value；
3) by Jing step 1) process after cation exchange resin and by step 2) obtained in impregnation liquid mixing after
Impregnated under vacuum；
4) cation exchange resin after terminate dipping is separated with impregnation liquid, and is dried, and obtains de- iodine
Resin sorbent.
2. method according to claim 1, it is characterised in that step 1) described in cation exchange tree
Fat is large hole cation exchanger resin and/or gel-network precipitation method, preferably macroporous cation exchange tree
Fat.
3. method according to claim 1 and 2, it is characterised in that step 1) described in vacuum locate in advance
Reason is carried out in Rotary Evaporators, and treatment conditions are：Vacuum<0.001MPa, temperature are 50-100 DEG C, place
The reason time is 1-5h；Then it is down to 20-50 DEG C, is preferably dropped to room temperature.
4. the method according to any one in claim 1-3, it is characterised in that step 2) described in
The aqueous solution of soluble silver salt is the aqueous solution of silver nitrate and/or silver acetate, and is come using nitric acid and/or acetic acid
Adjust pH.
5. the method according to any one in claim 1-4, it is characterised in that step 3) leaching
The immersion condition of stain is：Vacuum<0.001MPa, temperature are 20-100 DEG C, are preferably 40-80 DEG C, dipping
Time is 4-10h, is preferably 4-6h, rotary speed>100r/h.
6. the method according to any one in claim 1-5, it is characterised in that step 4) described in
It is separated into and is separated by filtration and/or centrifugation；
Also, step 4) described in drying be at 80-150 DEG C, be preferably dried 5-36h at 105-115 DEG C,
It is preferred that 11-13h.
7. the method according to any one in claim 1-6, it is characterised in that in step 1) it is described
Pretreatment and step 3) described in dipping during, keep vacuum to be less than 0.0001MPa, and walk
It is rapid 1) in the vacuum of preprocessing process be not less than step 3) in dipping process vacuum,
Also, step 1) described in the temperature of vacuum pre-treatment be 40-80 DEG C, preferably not less than step 3) institute
State the dipping temperature of dipping.
8. iodine resin adsorbent is taken off obtained in the method according to any one in claim 1-7.
9. iodine resin adsorbent is taken off obtained in the method according to any one in claim 1-7 in removing
Application in terms of iodine, preferably removes content in organic acid, preferred acetic acid<Application in terms of the iodine of 1ppm, more
It is preferred that removing content in oxo synthesis are obtained acetic acid<Application in terms of the iodine of 1ppm.
10. application according to claim 9, it is characterised in that by the organic acid containing iodide ion, preferably
Acetic acid with 1-30BV/h, the flow velocity of preferred 5-15BV/h, 20-80 DEG C, preferably pass through at 40-60 DEG C
The de- iodine resin adsorbent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510616297.9A CN106552596A (en) | 2015-09-24 | 2015-09-24 | A kind of de- iodine resin adsorbent and its preparation method and application |
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|---|---|---|---|
| CN201510616297.9A CN106552596A (en) | 2015-09-24 | 2015-09-24 | A kind of de- iodine resin adsorbent and its preparation method and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583628A (en) * | 2017-10-27 | 2018-01-16 | 王泽山 | A kind of acetic acid takes off the production technology of iodine silver resin adsorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0196173A1 (en) * | 1985-03-07 | 1986-10-01 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| CN103122043A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of deiodination agent |
| CN104645931A (en) * | 2013-11-22 | 2015-05-27 | 北京有色金属研究总院 | Preparation method of highly homogeneous Pd-loaded diatomite composite material |
-
2015
- 2015-09-24 CN CN201510616297.9A patent/CN106552596A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0196173A1 (en) * | 1985-03-07 | 1986-10-01 | Celanese Corporation | Removal of iodide compounds from non-aqueous organic media |
| CN103122043A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of deiodination agent |
| CN104645931A (en) * | 2013-11-22 | 2015-05-27 | 北京有色金属研究总院 | Preparation method of highly homogeneous Pd-loaded diatomite composite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583628A (en) * | 2017-10-27 | 2018-01-16 | 王泽山 | A kind of acetic acid takes off the production technology of iodine silver resin adsorbent |
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Application publication date: 20170405 |