CN101209409A - Silver-carrying macromolecule deriving carbon iodine-removing adsorption agent and preparation and application - Google Patents
Silver-carrying macromolecule deriving carbon iodine-removing adsorption agent and preparation and application Download PDFInfo
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Abstract
The invention discloses a carbon derivate sorbent which has silver-carrier macromolecules and is used for removing iodine and uses carbonized polymer as a carrier, and silver load occupies 0.1-2 percent of total weight of the sorbent, the granularity of the polymer is 20-100 meshes. The preparation method of the sorbent is as follows: small polymer spheres are prepared through the suspension polymerization of polyvinylidene chloride, carbonized, stewed by acetic acid, dried, loaded with silver compounds by using the solution impregnation method, and finally communicated with hydrogen for heating up and restoring, thus yielding the sorbent. The sorbent can be used for removing the iodine and the iodide of organic mediums, and the liquid phase method or the gas chromatographic method can be taken as operation ways, when using the liquid phase method for removing the iodine, liquid hourly space velocity is 1 to 15hr<-1>, and when using the gas chromatographic method for removing the iodine, liquid hourly space velocity is 1-20hr<-1> according to a liquid-processing capacity meter. With acetic acid as an organic medium, the control temperature of an adsorptive bed layer is 20 -110 DEG C when using the liquid phase method and the temperature of the adsorptive bed layer is 120- 350 DEG C when using the gas chromatographic method. The sorbent can reduce iodine ions in the acetic acid below 1 ppb.
Description
Technical field
The invention belongs to the chemical separating field, relate to a kind of silver-carrying macromolecule deriving carbon iodine-removing adsorption agent.
The invention still further relates to the preparation method of above-mentioned silver-carrying macromolecule deriving carbon iodine-removing adsorption agent.
The invention still further relates to the application of above-mentioned silver-carrying macromolecule deriving carbon iodine-removing adsorption agent.
Background technology
The removal of Iodide Ion is the work that big industrial application value is arranged in the organic media.Because the rhodiums of using as catalyst more in the carbonylating process; with the iodomethane is co-catalyst; and in the current technology of carbonylation of methanol production acetic acid and methyl acetate carbonylation production aceticanhydride, also to add the lithium iodide of big content usually, this certainly will bring the removal problem of iodine in the product.Because the advantage of raw material and cost, carbonylating process have now become the main flow technology that acetic acid and aceticanhydride are in the world produced, also become an industrial problem that is ubiquitous so remove iodine in acetic acid and the aceticanhydride medium.
Although can remove most iodide by traditional distillation, rectifying or chemical treatments, iodide that still can remaining trace in the product.Iodine in the acetic acid mainly exists with the form of iodide ion.Owing to all use noble metal catalyst in many production processes in the downstream product of acetic acid, such as with acetic acid being the catalyst that raw material is produced vinylacetate, the existence of iodine can make its poisoning, reduce even destroy its catalytic performance, so the existence of the iodide of these traces has limited the application by the synthetic acetate products of carbonylating process.Iodide ion content in the industrial acetic acid more than 20ppb, must drop to its content an enough low scope usually in some applications, will be lower than 10ppb usually.
The main flow research method in this field by the iodide ion in the silver ion adsorbing medium, is removed it then for using the ion-exchanger load silver ion from medium now.Therefore, research emphasis just concentrates on ion-exchanger and carries in the research and development of silver-colored technology, and ion-exchanger is mainly ion exchange resin and molecular sieve, now is described below respectively:
1) ion exchange resin
Carry out ion-exchange by ion exchange resin and Ag-containing solution, 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.Ion exchange resin has the ability than metals 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.But still there is not bibliographical information to solve its problem that recycles at present.Ion exchange resin must be than higher except that the cost of iodine technology like this.
The problem of selecting this ion exchange resin to consider mainly contains: under more stable under the acid condition, this condition strong, the suitable pore structure of the exchange capacity of silver ion is convenient to contact with media flow etc.Usually before ion exchange resin uses, to treat Treatment Solution and filter, to remove organic iodine impurity wherein with absorbent charcoal material.
2) molecular sieve
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 Kulprathipanja 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.And this has increased cost for the practical application that the ion-exchanger method is removed the iodine technology undoubtedly, has also brought inconvenience.
In addition, also have the people that the iodine in the absorbent charcoal material absorption organic media has been carried out studying (WO94/22804), this method can effectively be removed molecular iodine, but bad to the removing effect of trace iodine.Also there is the researcher to investigate active carbon adsorbs alkyl iodide under gas phase condition situation (US patent0010363), can reaches reasonable effect, iodide ion is not but had desirable removing effect.
Summary of the invention
The object of the present invention is to provide a kind of silver-carrying macromolecule deriving carbon iodine-removing adsorption agent.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned silver-carrying macromolecule deriving carbon iodine-removing adsorption agent.
For achieving the above object, silver-carrying macromolecule deriving carbon iodine-removing adsorption agent provided by the invention is a carrier with the polymer after the carbonization, and the load capacity of silver is the 0.1-2% of adsorbent gross weight, and the granularity of polymer is the 20-100 order.
Described silver-carrying macromolecule deriving carbon iodine-removing adsorption agent, wherein, silver-colored load capacity is the 0.2-0.8% of adsorbent gross weight.
Described silver-carrying macromolecule deriving carbon iodine-removing adsorption agent, wherein, the granularity of polymer is the 60-80 order.
The method of the above-mentioned silver-carrying macromolecule deriving carbon iodine-removing adsorption agent of preparation provided by the invention, its step is as follows:
A) with the vinylidene chloride be monomer, azodiisobutyronitrile is an initator, is added in the saturated aqueous sodium sulfate to stir, and the mol ratio of initator and monomer is 1%;
B) with the bentonite be template agent and dispersant, add in the suspension of steps A that the addition of bentonite is the 5-15% of monomer volume, stir, be warming up to 35-40 ℃, kept 10-15 hour, obtain granulated polymer;
C) polymer that obtains of step B carries out carbonization, and the carbonization condition is: 160-180 ℃ of carbonization degassing 12～20 hours, 300-600 ℃ carbonization 3-6 hour, 800-1000 ℃ carbonization 1-2 hour, the polymer after the carbonization;
D) polymer that step C is made is put into silver nitrate or silver acetate solution, is stirred to solution and all is aggregated the thing absorption, and the load capacity of silver is the 0.1-2% of adsorbent gross weight; This silver nitrate or silver acetate solution are water, methyl alcohol or acetonitrile solution;
E) methyl alcohol in the polymer of step D is vapored away, feed hydrogen then and reduce, reduction temperature is 150-200 ℃, and the recovery time is 1-5 hour, promptly makes target product.
Described preparation method, wherein, polymerization inhibitor is wherein removed in the distillation before reaction of the vinylidene chloride in the steps A.
Described preparation method, wherein, the bentonite water furnishing pasty state among the step B.
Described preparation method, wherein, mixing speed is 300rpm.
Described preparation method, wherein, the granulated polymer that step B obtains boils removing unnecessary bentonite powder with boiling water, and with the hot acetone washing removing unreacted monomer, and then continue step C.
Silver-carrying macromolecule deriving carbon iodine-removing adsorption agent provided by the invention can be used for removing the organic media iodide, and when liquid phase method removed iodine, liquid hourly space velocity (LHSV) was 1-15hr
-1, the liquid hourly space velocity (LHSV) in the treat liquid ability when vapor phase method removes iodine is 1-20hr
-1Wherein, the iodide in the organic media are organic iodide and inorganic iodide, are particularly useful for removing the Iodide Ion in the acetic acid.
The specific embodiment
The present invention is used for removing the method for organic solvent iodide, is mainly used in organic iodide and the inorganic iodide removed in the organic solvent, is particularly useful for removing the Iodide Ion in the acetic acid.The present invention adopts a kind of silver-carrying macromolecule deriving carbon iodine-removing adsorption agent, makes to contain organic solvent by the adsorption column of this adsorbent is housed, and removes iodide wherein.
Preparation of adsorbent method of the present invention is: make polymer globules by vinylidene chloride suspension polymerisation, the acetic acid boiling will be used after its carbonization, the purpose of boiling is the material that can be dissolved in organic solvent on it in order to remove, in the time of can avoiding it to use like this to the pollution of organic solvent, simultaneously can reduce or avoid coming off of silver, after the bead drying after the boiling, with the compound of silver in the solution dipping method load, logical then hydrogen heating reduction and making.The granularity for preparing the used polymer globules of this adsorbent is the 20-100 order, and wherein the adsorbent that makes of 60-80 purpose polymers bead has the optimum iodine effect of removing.The carbonisation of polymer globules is: 160-180 ℃ of carbonization degassing 12-20 hour, 300-600 ℃ carbonization 3-6 hour, 800-1000 ℃ carbonization 1-2 hour.The compound of the silver that infusion process load when silver is used is silver nitrate or silver acetate, and used solvent is water, methyl alcohol, acetonitrile, and the load capacity of silver is 0.1-2.0%, and wherein silver-colored load capacity has the optimum iodine effect of removing during for 0.2-0.8%.The reduction temperature of logical hydrogen is 150-200 ℃, and the recovery time is 1-5 hour.
This adsorbent can be used for removing iodine and the iodide in the organic media, and mode of operation can adopt liquid phase method, also can adopt vapor phase method.When liquid phase method removed iodine, liquid hourly space velocity (LHSV) was 1-15hr
-1, the liquid hourly space velocity (LHSV) in the treat liquid ability when vapor phase method removes iodine is 1-20hr
-1
When organic media was acetic acid, the control temperature of liquid phase method adsorption bed was 20-110 ℃, and vapor phase method adsorption bed temperature is 120-350 ℃.
Below by embodiment the present invention is further set forth, but be not limited in listed examples.
Embodiment 1:
Polymerization inhibitor is removed in the vinylidene chloride distillation obtained monomer, initator is an azodiisobutyronitrile, and its consumption is 1% (mol ratio) of monomer consumption, is template agent and dispersant with the bentonite, water furnishing pasty state before bentonite uses, the polymerization of macromolecule bead is suspension polymerisation.Add monomer and initator in saturated aqueous sodium sulfate, the control mixing speed is 350-400rpm, stirs to add an amount of dispersant after 10 minutes, temperature is risen to 40 ℃, and kept 15 hours, obtains the polymer of 40-80 purpose small spherical particles shape.This polymer is boiled removing unnecessary bentonite powder with boiling water, and with the hot acetone washing to remove unreacted monomer.
With the polymer screening that obtains; and take out wherein 60 purposes and partly put into quartz ampoule, be warming up to 180 ℃ and kept 15 hours under the argon shield, rise to 300 ℃ and kept 3 hours then gradually; be warming up to 600 ℃ and kept 3 hours again, be warming up to 1000 ℃ and kept 2 hours then gradually.Promptly get carbonized polymers.
Get the carbonized polymers 20g that makes, the 0.1575g silver nitrate is dissolved in the 22.5ml methyl alcohol, drop into carbonized polymers in the methanol solution and stirring rapidly, all being carbonized polymer until solution sponges, carbonized polymers is all soaked into and is stayed without any liquid at this moment, carbonized polymers behind the dipping is placed air, all vapor away up to wherein methyl alcohol, put it into then and feed hydrogen in the quartz ampoule, and be warming up to 150 ℃ of maintenances 2 hours, promptly make the silver-carrying macromolecule deriving carbon adsorbent.
Embodiment 2:
The adsorbent 10ml that embodiment 1 the is made internal diameter of packing into is as adsorption column in the stainless steel tube of 8mm, one end of steel pipe dress adsorbent connects condenser to collect liquid behind the post, the other end leaves the space of 20ml, mineral wool boiled with acetic acid later fill up this space, link to each other with microprocessor pump drive then as vaporizer.Adsorption column and vaporizer are warming up to 300 ℃, the acetic acid of iodide ion content 35ppb are squeezed into adsorption column with pump, liquid sample determination iodide ion concentration behind the flow velocity of change pump and the difference post:
| Liquid hourly space velocity (LHSV) (hr -1) | 2 | 10 | 15 | 20 |
| Liquid iodide ion (ppb) behind the post | 0.033 | 0.129 | 0.267 | 0.634 |
Embodiment 3:
Adsorption column among the embodiment 2 is controlled at 25 ℃, the acetic acid of iodide ion content 35ppb is squeezed into adsorption column with pump, change the flow velocity of pump and get tail washings sample determination iodide ion concentration respectively:
| Liquid hourly space velocity (LHSV) (hr -1) | 3 | 10 | 15 |
| Liquid iodide ion (ppb) behind the post | 0.028 | 0.324 | 0.768 |
Claims (10)
1. a silver-carrying macromolecule deriving carbon iodine-removing adsorption agent is a carrier with the polymer after the carbonization, and the load capacity of silver is the 0.1-2% of adsorbent gross weight, and the granularity of polymer is the 20-100 order.
2. silver-carrying macromolecule deriving carbon iodine-removing adsorption agent as claimed in claim 1, wherein, silver-colored load capacity is the 0.2-0.8% of adsorbent gross weight.
3. silver-carrying macromolecule deriving carbon iodine-removing adsorption agent as claimed in claim 1, wherein, the granularity of polymer is the 60-80 order.
4. method for preparing the described silver-carrying macromolecule deriving carbon iodine-removing adsorption agent of claim 1, its step is as follows:
A) with the vinylidene chloride be monomer, azodiisobutyronitrile is an initator, is added in the saturated aqueous sodium sulfate to stir, and the mol ratio of initator and monomer is 1%;
B) with the bentonite be template agent and dispersant, add in the suspension of steps A that the addition of bentonite is the 5-15% of monomer volume, stir, be warming up to 35-40 ℃, kept 10-15 hour, obtain granulated polymer;
C) polymer that obtains of step B carries out carbonization, and the carbonization condition is: 160-180 ℃ of carbonization degassing 12～20 hours, 300-600 ℃ carbonization 3-6 hour, 800-1000 ℃ carbonization 1-2 hour, the polymer after the carbonization;
D) polymer that step C is made is put into silver nitrate or silver acetate solution, is stirred to solution and all is aggregated the thing absorption, and the load capacity of silver is the 0.1-2% of adsorbent gross weight; This silver nitrate or silver acetate solution are water, methyl alcohol or acetonitrile solution;
E) methyl alcohol in the polymer of step D is vapored away, feed hydrogen then and reduce, reduction temperature is 150-200 ℃, and the recovery time is 1-5 hour, promptly makes target product.
5. preparation method as claimed in claim 4, wherein, polymerization inhibitor is wherein removed in the distillation before reaction of the vinylidene chloride in the steps A.
6. preparation method as claimed in claim 4, wherein, the bentonite water furnishing pasty state among the step B.
7. preparation method as claimed in claim 4, wherein, mixing speed is 300rpm.
8. preparation method as claimed in claim 4, wherein, the granulated polymer that step B obtains boils removing unnecessary bentonite powder with boiling water, and with the hot acetone washing removing unreacted monomer, and then continue step C.
9. the application of each described silver-carrying macromolecule deriving carbon iodine-removing adsorption agent iodide in removing organic media among the claim 1-3, when liquid phase method removed iodine, liquid hourly space velocity (LHSV) was 1-15hr
-1, the liquid hourly space velocity (LHSV) in the treat liquid ability when vapor phase method removes iodine is 1-20hr
-1
10. application as claimed in claim 9, wherein, the iodide in the organic media are organic iodide and inorganic iodide.
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| CN102000546A (en) * | 2010-11-11 | 2011-04-06 | 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 |
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| CN103831087A (en) * | 2012-11-20 | 2014-06-04 | 株式会社东芝 | Iodine adsorbent, tank for water treatment, and iodide compound treatment system |
| CN104874356A (en) * | 2014-02-27 | 2015-09-02 | 株式会社东芝 | Iodine adsorbent, water treatment tank, iodine adsorbing system and method for manufacturing the iodine adsorbent |
| CN105688807A (en) * | 2016-01-21 | 2016-06-22 | 广西大学 | Preparation method of micro-pore type active carbon adsorbed by organic iodine |
| CN112023874A (en) * | 2020-09-18 | 2020-12-04 | 上海复旭分子筛有限公司 | Zeolite molecular sieve adsorbent for deeply removing iodide in gas-phase medium and preparation method and application thereof |
| CN114713207A (en) * | 2022-04-07 | 2022-07-08 | 江苏索普聚酯科技有限公司 | Functional adsorption material for recovering iodine and rhodium elements in organic acetic acid and preparation method thereof |
| CN115569634A (en) * | 2022-10-27 | 2023-01-06 | 中盐常州化工股份有限公司 | Iodine-removing carbon adsorption material for preparing ionic membrane caustic soda and preparation method thereof |
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| US4615806B1 (en) * | 1985-03-07 | 1994-05-03 | Hoechst Co American | Removal of iodide compounds from non-aqueous organic media |
| US5962735A (en) * | 1998-03-06 | 1999-10-05 | Uop Llc | Method for treating an organic liquid contaminated with an iodide compound |
| EP1114814A3 (en) * | 1999-12-29 | 2003-01-22 | Haldor Topsoe A/S | Method for the reduction of iodine compounds from a process stream |
| CN100509138C (en) * | 2004-12-21 | 2009-07-08 | 上海焦化有限公司 | Sorbent of zeolite with carrying silver, preparation method and application thereof |
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| 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 |
| CN103831087A (en) * | 2012-11-20 | 2014-06-04 | 株式会社东芝 | Iodine adsorbent, tank for water treatment, and iodide compound treatment system |
| CN103263916A (en) * | 2013-04-24 | 2013-08-28 | 浙江大学 | Preparation method and use of crosslinked polyethylene-loaded metal nanoparticles |
| CN103263916B (en) * | 2013-04-24 | 2016-01-06 | 浙江大学 | The preparation method that crosslinked polyethylene is metal nanoparticles loaded and application |
| CN104874356A (en) * | 2014-02-27 | 2015-09-02 | 株式会社东芝 | Iodine adsorbent, water treatment tank, iodine adsorbing system and method for manufacturing the iodine adsorbent |
| CN105688807A (en) * | 2016-01-21 | 2016-06-22 | 广西大学 | Preparation method of micro-pore type active carbon adsorbed by organic iodine |
| CN112023874A (en) * | 2020-09-18 | 2020-12-04 | 上海复旭分子筛有限公司 | Zeolite molecular sieve adsorbent for deeply removing iodide in gas-phase medium and preparation method and application thereof |
| CN114713207A (en) * | 2022-04-07 | 2022-07-08 | 江苏索普聚酯科技有限公司 | Functional adsorption material for recovering iodine and rhodium elements in organic acetic acid and preparation method thereof |
| 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 |
| CN115569634A (en) * | 2022-10-27 | 2023-01-06 | 中盐常州化工股份有限公司 | Iodine-removing carbon adsorption material for preparing ionic membrane caustic soda and preparation method thereof |
| CN116393107A (en) * | 2023-03-16 | 2023-07-07 | 中国辐射防护研究院 | Preparation method and application of silver-silicon composite aerogel |
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Effective date of registration: 20200121 Address after: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Co-patentee after: Jiangsu Sopo Chemical Co.,Ltd. Patentee after: Institute of Chemistry, Chinese Academy of Sciences Address before: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Co-patentee before: Jiangsu Soap (Group) Co., Ltd. Patentee before: Institute of Chemistry, Chinese Academy of Sciences |