CN101209428B - Adsorption agent for removing iodide from organic medium and preparation and application - Google Patents
Adsorption agent for removing iodide from organic medium and preparation and application Download PDFInfo
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- CN101209428B CN101209428B CN200610169739A CN200610169739A CN101209428B CN 101209428 B CN101209428 B CN 101209428B CN 200610169739 A CN200610169739 A CN 200610169739A CN 200610169739 A CN200610169739 A CN 200610169739A CN 101209428 B CN101209428 B CN 101209428B
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Abstract
The invention provides a sorbent used for removing iodide in organic medium, in particular to macroporous crosslinking ion exchange resin loaded with one or a plurality of metal ions. The metal ions loaded is one of silver, Hg and Pd, and mol loading of the metal ions is 1-90 percent of active sites of the ion exchange resin; the macroporous crosslinking ion exchange resin comprises two functionalgroups containing sulfonic group and carboxyl. A preparation method of the invention is that: through the initiation of azo-bis-iso-heptonitrile, acrylonitrile is suspension copolymerized with divinylbenzene monomer to obtain corsslinking polymer beads, pore-forming agent of which is extracted and washed out by solvent, thus obtaining the invention through sulfonation and ion exchange loading metal ions; the mol loading of the metal ions is 1-90 percent of the active sites of the ion exchange resin. Ceiling temperature used by the sorbent is 90 DEG C, liquid hourly space velocity is 1-15hr<-1> when ion-exchange column is used for removing iondine. The sorbent can remove the iondine ions in acetic acid below 5ppb.
Description
Technical field
The present invention relates to a kind of adsorbent that is used for removing the organic media iodide.
The invention still further relates to above-mentioned preparation of adsorbent method.
The invention still further relates to the application of above-mentioned adsorbent.
Background technology
Contain iodide in the organic media and can bring some problems in its use, especially in catalytic reaction process, the existence of iodine can make some noble metal catalysts poison.As everyone knows, the main flow technology of producing acetic acid is all methanol carbonylation of rhodium series catalyzer to catalyse of Mengshan, and iodomethane is essential co-catalyst in this technology.Celanese company on its basis by add the lithium iodide of high-load in catalyst system and catalyzing, has further improved production capacity and has suppressed water gas reaction again, has reduced the loss of raw material.The existence in reaction system of iodomethane and lithium iodide contains the iodide of high level in the acetate products of make producing.These iodide, especially iodide ion, in follow-up separating technology, be difficult to Ex-all, this is with regard to for to have introduced trouble with acetic acid as the production technology of raw material, relatively distinct issues are in the production technology by acetic acid and ethylene production vinylacetate, and used catalyst is responsive to the non-product of iodide.Therefore, seek a kind of feasible and economic method and remove iodide in the organic solvent, be the actual needs of Chemical Manufacture, and people remove the technical exploration of also having carried out of iodine at solvent.Iodide ion content is more than the 20ppb in the industrial acetic acid product, satisfies the needs of more production technologies for making acetate products, its iodide ion content need be dropped to below the 10ppb even lower.Usually iodide ion concentration is low more in the organic media, and it is big more to remove the iodine difficulty.
Carry out ion-exchange by ion exchange resin and Ag-containing solution, can make the silver-colored type ion exchange resin that can be used for adsorbing iodide ion, a lot of researchers are exploring aspect this, and have obtained some progress.The Hilton of Celanese company, people (US patent 4615806) such as Charles B have prepared the macro porous crosslinking strongly acidic cation-exchange, the gel-type that this resin is different from the past, has better hydrodynamic performance, this resin is more stable under acid condition, and the active site with at least 1% is converted into the form of silver or mercury, and wherein 25-75% is the form of silver.The researcher is with the anion exchange resin Amberlite.RTM.IERA 45 in this resin and Japan Patent (Japanese Pat.No.7337762) technology, Amberlyst.RTM 15 and have the Amberlite RTM.IRA 900 of quaternary ammonium group and the mixed adsorbent of active carbon compares has proved the advantage of this technology.The Fish of Union Carbide Corporation, people such as Barry B. have developed a kind of ion exchange resin (US Patent 767487) that contains mercapto, and exchange with mercapto and silver, mercury or palladium, this resin is skeleton with the macroporous polystyrene, this technology remove the iodine effect also relatively significantly.
The technology of removing iodine by the ion exchange resin method is more in addition, such as: GB2112394A, US patent 4615806, EP 296854, EP 0196173A etc.Ion exchange resin has the ability than metal ions such as the better load silver of molecular sieve, and better hydrodynamic performance can be arranged, and it is more satisfactory that the one way of this technology is removed the iodine effect.
It also is a kind of main stream approach in this field that molecular sieve removes iodine as the ion-exchanger load silver ion, and many people also study these class methods.Relatively be typically the Kulprathipan ja of UOP LLC, people's such as Santi work (US patent 5962735), they remove the iodine method to silver molecular sieve and compare comprehensive research and argumentation.They are ion-exchanger with the zeolite molecular sieve (Y zeolite, LZ-210, Y-85, and their mixture) of Silicon-rich, by a kind of porous and also under adsorption conditions stable inorganic oxide adhesive be shaped and make.This ion-exchanger passes through metal and their mixtures such as exchange silver, mercury, copper, lead, thallium, palladium, and has the ability except that iodide ion, and wherein silver is first-selected metal, and LZ-210 is first-selected molecular sieve.The optional aluminium oxide of adhesive, silica, zirconia, chromium oxide, vanadium oxide, magnesia and their mixture.This adsorbent need calcined more than 500 ℃ before carrying out cation exchange.The use of can regenerating of this molecular sieve, method are the mixtures that feeds hydrogen or hydrogen and indifferent gas between 350-600 ℃.Because it is unstable at the medium that has to be used for the adhesive of bonding molecular sieve, generated gel by medium dissolves easily, so the organic media of handling through molecular sieve also needs a post-processing step sometimes, to remove by impurity such as its aluminium oxide that dissolves away and silica.
Owing to contain a certain amount of metal ion usually in the pending medium, these ions may come from the loss of the alloy in catalyst, reactor and the process equipment, they have the ability of the silver ion on the displacement ion-exchanger, so ion-exchange-resin process and sieve method have just all run into an intrinsic problem, the i.e. losing issue of silver ion.Therefore, if these two kinds of main flow iodine-removing adsorption agents drop into practical application, all need an additional step: before carrying silver-colored adsorbent, will add one section ion-exchanger usually, to remove the metal ion in the medium.
Summary of the invention
The object of the present invention is to provide a kind of adsorbent that is used for removing the organic media iodide.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned adsorbent.
For achieving the above object, the adsorbent that is used for removing the organic media iodide provided by the invention, macro porous crosslinking type ion exchange resin for one or more metal ions of load, the metal ion of load is a kind of in silver, mercury, the palladium, and the mole load capacity of metal ion is the 1-90% of ion exchange resin active sites;
Contain sulfonic group and two kinds of functional groups of carboxyl in the described macro porous crosslinking type ion exchange resin.
Described adsorbent, wherein, the metal ion of load is a silver.
Described adsorbent, wherein, the mole load capacity of metal ion is the 20-70% of ion exchange resin active sites.
The method of the above-mentioned adsorbent of preparation provided by the invention, its step is as follows:
A) reaction raw materials, pore creating material and initator are added to the Na of 8-10%
2SO
4In the aqueous solution, stir under the room temperature-40 ℃;
Wherein: reaction raw materials is acrylonitrile and divinylbenzene, acrylonitrile: the weight ratio of divinylbenzene=1: 1-10;
Pore creating material is one or several of kerosene, toluene, gasoline, fatty alcohol, and the addition of pore creating material is the 50-120% of reaction raw materials gross weight, if pore creating material is multiple mixture, needs to keep toluene level be not less than 30%, and all the other ratios can be allocated arbitrarily;
Initator is an ABVN, and its additional proportion is the 1-3% of reaction raw materials gross weight;
B) add dispersant and condensation polymer, stir, and be warming up to 60-70 ℃, reacted 18-24 hour;
Wherein dispersant is nine soil, and its additional proportion is the 5-15% of reaction raw materials cumulative volume;
Condensation polymer is TEPA-epoxychloropropane, and its additional proportion is the 1-3% of reaction raw materials gross weight;
C) product of step B is used acetone extracting 30-48 hour, and flush away pore creating material wherein promptly gets macro porous crosslinking macromolecule bead;
D) the macro porous crosslinking macromolecule bead that step C is made adds excessive oleum and carries out sulfonation, is warming up to 70-80 ℃, stirs sulfonating reaction 6-8 hour down;
E) stir down, step D reactant mixture is added in the entry, bead sinks under water, and removes the acid solution on upper strata with decantation, is washed to neutrality, promptly gets strong acid ion exchange resin;
F) get the strong acid ion exchange resin that step e makes and be soaked in the metal ion aqueous solution of silver, mercury or palladium, stirred 8-10 hour under the lucifuge, promptly get target product.
Described preparation method, wherein, acrylonitrile: the weight ratio of divinylbenzene=1: 8-9.
Described preparation method, wherein, polymerization inhibitor is wherein removed in the decompression distillation before reaction of the acrylonitrile in the steps A; Divinylbenzene washes with water to remove water-soluble polymerization inhibitor wherein.
Described preparation method, wherein, the dispersant water furnishing pasty state among the step B.
The preparation method of institute's art, wherein, mixing speed is 300rpm.
Adsorbent provided by the invention can be used for removing iodide in the organic media, and the ceiling temperature that this adsorbent uses is 90 ℃, and liquid hourly space velocity (LHSV) is 1～15hr when removing iodine in the ion exchange column mode
-1
Described organic media is organic acid, especially acetic acid.
Adsorbent of the present invention has been introduced the itrile group with strong electron-withdrawing power and polarity, it with carry silver-colored sulfonic acting in conjunction and make this adsorbent have the better iodine effect of removing.
The specific embodiment
Adsorbent provided by the invention is the macro porous crosslinking type ion exchange resin of one or more metal ions of load, and the metal ion of load is a kind of in silver, mercury, the palladium, wherein silver ion to remove the iodine effect best.The mole load capacity of metal ion is the 1-90% of ion exchange resin active sites, preferably 20-70%.Contain two kinds of functional groups of sulfonic group and carboxyl in the ion exchange resin.
The method of the above-mentioned adsorbent of preparation provided by the invention is as follows:
Under the initiation of ABVN, obtain globules of cross-linked polymers by acrylonitrile and divinylbenzene suspension copolymerization, by solvent extraction flush away pore creating material wherein, then through sulfonation, exchange metal ion and obtaining.The amount ratio of divinylbenzene and acrylonitrile is 1-10, and optimum amount is than being 7-9, and used pore creating material is kerosene, toluene, gasoline, fatty alcohol, alkane etc.The handled organic media of this adsorbent is mainly organic acid, especially acetic acid.This adsorbent is used for removing the organic iodide and the iodide ion of organic media, is particularly useful for removing iodide ion wherein.The ceiling temperature that this adsorbent uses is 90 ℃, can be used for reactor method, also can be used for the ion exchange column method, and liquid hourly space velocity (LHSV) is 1-15hr when wherein removing iodine in the ion exchange column mode
-1
If also contain other foreign ion in the organic media, especially high volence metal ion such as iron ion, be preferably in organic media and flow into and add the preceding paragraph ion exchange resin before this adsorbent, cause it to come off from resin because high volence metal ion replaces silver ion easily with exchange metal ion wherein.Also can add one section not silver resin in the adsorbent back, in the organic solvent of handling, run off to reduce silver ion.Iodide ion content is about 20ppb in the industrial acetic acid, and after this sorbent treatment, amount of iodine can drop to below the 5ppb.
Below by embodiment the present invention is further set forth, but be not limited in listed examples.
Embodiment 1:
The synthetic employing suspension polymerization of macromolecule bead.Reaction raw materials is divinylbenzene 54g, and acrylonitrile 6g, used pore creating material are kerosene 25g, toluene 25g, isoamyl alcohol 15g.Initator is ABVN 1.3g.Dispersant is the condensation polymer 1.2g of nine native 24g and TEPA-epoxychloropropane.
Wherein polymerization inhibitor is removed in the acrylonitrile decompression distillation, with divinylbenzene with distillation washing 3 times to remove water-soluble polymerization inhibitor wherein.With nine soil distilled water furnishing pasty state.10% Na about adding 480ml in the flask of 1000ml
2SO
4The aqueous solution, about 40 ℃ of water-bath temperature controls add aforesaid treated polymer monomer, pore creating material and initator in the flask, start mechanical agitation and control mixing speed 300rpm, stir to add nine soil and condensation polymer after 30 minutes, continue to stir 30 minutes.Bath temperature is slowly raise, and be controlled at 65-70 ℃, reacted 24 hours.React the back water cyclic washing that finishes, after poach, the extracting of usefulness acetone promptly got macro porous crosslinking macromolecule bead with flush away pore creating material wherein in 48 hours.
With adding an amount of dimethyl sulfoxide (DMSO) swelling after the macro porous crosslinking macromolecule bead drying that makes, add excessive oleum then and carry out sulfonation.Be warming up to 80 ℃, intermittently stir down sulfonating reaction 8 hours.Reactant mixture is slowly added in a large amount of distilled water of vigorous stirring, bead sinks under water, and removes the acid solution on upper strata with decantation, is washed to repeatedly near neutral, promptly gets strong acid ion exchange resin.Get in the 1.0mol/L silver nitrate aqueous solution that quantity of resin is soaked in 200ml, slowly stirred 10 hours under the lucifuge.Wash this resin repeatedly, till the sodium chloride solution detection water lotion with 0.1mol/L does not have muddiness.Promptly make the adsorbent that is used for removing the organic solvent iodide of the present invention.
Embodiment 2
With the adsorbent 10ml that embodiment 1 makes, the internal diameter of packing into is in the acid buret of 8mm, and by adsorption column, the control liquid hourly space velocity (LHSV) is 2hr in 35 ℃ of acetic acid that will contain iodide ion 25ppb down
-1, record behind the post that iodide ion content is 0.018ppb in the acetic acid.
Embodiment 3
With the adsorbent 10ml that embodiment 1 makes, the internal diameter of packing into is in the acid buret of 8mm, and by adsorption column, the control liquid hourly space velocity (LHSV) is 8hr in 30 ℃ of acetic acid that will contain iodide ion 25ppb down
-1, record behind the post that iodide ion content is 1.6ppb in the acetic acid.
Embodiment 4
With the adsorbent 10ml that embodiment 1 makes, the internal diameter of packing into is in the acid buret of 8mm, and by adsorption column, the control liquid hourly space velocity (LHSV) is 13hr in 25 ℃ of acetic acid that will contain iodide ion 25ppb down
-1, record behind the post that iodide ion content is 3.9ppb in the acetic acid.
Claims (10)
1. adsorbent that is used for removing the organic media iodide, macro porous crosslinking type ion exchange resin for one or more metal ions of load, the metal ion of load is a kind of in silver, mercury, the palladium, and the mole load capacity of metal ion is the 1-90% of ion exchange resin active sites;
Contain sulfonic group and two kinds of functional groups of carboxyl in the described macro porous crosslinking type ion exchange resin.
2. adsorbent as claimed in claim 1, wherein, the metal ion of load is a silver.
3. adsorbent as claimed in claim 1, wherein, the mole load capacity of metal ion is the 20-70% of ion exchange resin active sites.
4. method for preparing the described adsorbent of claim 1, its step is as follows:
A) reaction raw materials, pore creating material and initator are added to the Na of 8-10%
2SO
4In the aqueous solution, stir under the room temperature-40 ℃;
Wherein: reaction raw materials is acrylonitrile and divinylbenzene, acrylonitrile: the weight ratio of divinylbenzene=1: 1-10;
Pore creating material is one or several of kerosene, toluene, gasoline, fatty alcohol, and the addition of pore creating material is the 50-120% of reaction raw materials gross weight, and when wherein pore creating material was multiple mixture, toluene level was not less than 30%;
Initator is an ABVN, and its additional proportion is the 1-3% of reaction raw materials gross weight;
B) add dispersant and condensation polymer, stir, and be warming up to 60-70 ℃, reacted 18-24 hour;
Wherein dispersant is nine soil, and its additional proportion is the 5-15% of reaction raw materials cumulative volume;
Condensation polymer is TEPA-epoxychloropropane, and its additional proportion is the 1-3% of reaction raw materials gross weight;
C) product of step B is used acetone extracting 30-48 hour, and flush away pore creating material wherein promptly gets macro porous crosslinking macromolecule bead;
D) the macro porous crosslinking macromolecule bead that step C is made adds excessive oleum and carries out sulfonation, is warming up to 70-80 ℃, stirs sulfonating reaction 6-8 hour down;
E) stir down, step D reactant mixture is added in the entry, bead sinks under water, and removes the acid solution on upper strata with decantation, is washed to neutrality, promptly gets strong acid ion exchange resin;
F) get the strong acid ion exchange resin that step e makes and be soaked in the metal ion aqueous solution of silver, mercury or palladium, stirred 8-10 hour under the lucifuge, promptly get target product.
5. preparation method as claimed in claim 4, wherein, acrylonitrile: the weight ratio of divinylbenzene=1: 8-9.
6. preparation method as claimed in claim 4, wherein, polymerization inhibitor is wherein removed in the decompression distillation before reaction of the acrylonitrile in the steps A; Divinylbenzene washes with water to remove water-soluble polymerization inhibitor wherein.
7. preparation method as claimed in claim 4, wherein, the dispersant water furnishing pasty state among the step B.
8. preparation method as claimed in claim 4, wherein, mixing speed is 300rpm.
9. the application of each described adsorbent iodide in removing organic media among the claim 1-3, the ceiling temperature that this adsorbent uses is 90 ℃, liquid hourly space velocity (LHSV) is 1～15hr when removing iodine in the ion exchange column mode
-1
10. application as claimed in claim 9, wherein, organic media is an organic acid.
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| CN200610169739A CN101209428B (en) | 2006-12-28 | 2006-12-28 | Adsorption agent for removing iodide from organic medium and preparation and application |
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| CN200610169739A CN101209428B (en) | 2006-12-28 | 2006-12-28 | Adsorption agent for removing iodide from organic medium and preparation and application |
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| CN101209428A CN101209428A (en) | 2008-07-02 |
| CN101209428B true CN101209428B (en) | 2010-05-19 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000546B (en) * | 2010-11-11 | 2012-10-03 | 江苏索普（集团）有限公司 | Adsorbent for removing trace halides in gas as well as preparation method and application thereof |
| EP2658903B1 (en) * | 2010-12-30 | 2017-02-08 | Celanese International Corporation | Ion exchange resin composition for the purification of acetic acid product streams |
| CN103121934B (en) * | 2011-11-18 | 2014-07-23 | 中国石油化工股份有限公司 | Method for reducing iodide impurity content in acetic acid |
| CN102618057B (en) * | 2012-03-25 | 2014-02-05 | 徐志兵 | Ag/ion exchange resin composite material |
| CN103071546B (en) * | 2013-02-06 | 2014-12-24 | 中国石油化工股份有限公司 | Method for separating chloride ions in produced liquid of oil field |
| CN108014742B (en) * | 2017-11-29 | 2021-01-05 | 北京科技大学 | Method for selectively and deeply removing trace silver ions in tail liquid |
| CN114713207B (en) * | 2022-04-07 | 2024-03-15 | 江苏索普聚酯科技有限公司 | Functional adsorption material for recycling iodine and rhodium elements in organic acetic acid and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071662A (en) * | 1991-10-18 | 1993-05-05 | 英国石油化学品有限公司 | From carboxylic acid and carboxylic acid anhydride, remove the method for iodide |
| CN1205709A (en) * | 1995-12-21 | 1999-01-20 | Iab离子交换器股份有限公司 | Process for prepn. of very acidic cation exchangers |
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2006
- 2006-12-28 CN CN200610169739A patent/CN101209428B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071662A (en) * | 1991-10-18 | 1993-05-05 | 英国石油化学品有限公司 | From carboxylic acid and carboxylic acid anhydride, remove the method for iodide |
| CN1205709A (en) * | 1995-12-21 | 1999-01-20 | Iab离子交换器股份有限公司 | Process for prepn. of very acidic cation exchangers |
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Effective date of registration: 20200131 Address after: 212006 No. 88 Qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province Co-patentee after: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee after: Jiangsu Sopo Chemical Co.,Ltd. Address before: 212006 Long Gang, Dantu, Jiangsu, Zhenjiang Co-patentee before: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee before: Jiangsu Soap (Group) Co., Ltd. |