CN101829542A - High silver supported zeolite molecular sieve acetate deiodinase adsorber and preparation method thereof - Google Patents
High silver supported zeolite molecular sieve acetate deiodinase adsorber and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the chemical technical field and relates to a high silver supported zeolite molecular sieve acetate deiodinase adsorber and a preparation method thereof. In the adsorber, the sizes of zeolite cavity openings are respectively 0.66*0.71 nanometers and 0.56*0.56 nanometers, and the adsorber is provided with characteristic X-ray diffraction lines in a BEA (Background Equivalent Activity) type zeolite structure. The deiodinase adsorber is prepared by the steps that saled sodium type zeolite molecular sieve powder with two-dimensional twelve oygen membered ring cavity openings is formed through binder, is in in-situ hydrothermal strengthening treatment to generate chemical bonds and then is treated by ion exchange sodium removal and silver carrying. The adsorber has the advantages of high crystallization degree, strong particle strength, high silver supported and strong adsorption capacity to organic iodide, inorganic iodide and molecular iodide with different sizes contained in strong acidic medium, can enable the total iodide content in product acetic acid after deiodination treatment by the adsorber to be lower than 5ppb and is suitable for being used as raw materials for synthetizing vinyl acetate.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of be used for that the synthetic carboxylic acid of carbonylation or carboxylic acid anhydrides product technology removes iodide take off iodine zeolite adsorbent and preparation method thereof.
Background technology
Because of using iodide to do catalyst aid, inevitably there is the iodide or derivatives thereof in the carboxylic acid of production or the carboxylic acid anhydrides product in the technology of synthetic carboxylic acid of carbonylation or carboxylic acid anhydrides.Through traditional distillation, rectifying or with certain chemical treatments, iodide (derivative) that still can remaining trace are difficult to remove.Its existence has limited the application of the product of producing with this method.Particularly can not be used in the production process of metal of using the iodine sensitivity as catalyst.In the process as acetic acid and ethylene production vinyl acetate, require the total content of iodine in the acetic acid to be lower than at least below the 10ppb, be preferably lower than 5ppb.
Propose among the world patent WO 94/22804 to remove hydrogen iodide and molecular iodine with NACF.With usual way NACF is made a filter, make to contain iodine acetic acid by this filter, NACF is just with iodine molecule and hydrogen iodide adsorption removal.Though this method is better to the removing effect of hydrogen iodide and molecular iodine, is not easy Ex-all organic iodine and molecular iodine, and total content of iodine is dropped to below the 10ppb.
When U.S. Pat 2002/0010363 is found will to contain the acetic acid of alkyl iodide and metal acetate class in being dispersed in active carbon is contacted in gas phase under high temperature and normal pressure, alkyl iodide changes corresponding alkyl acetate into, and iodide are bonded on the adsorbent with inorganic (non-volatile) iodide form and can effectively remove alkyl iodide.This method not only energy consumption is big, and inorganic iodine is not removed effect.
U.S. Pat 4,615,806 propose with the iodide in the macroreticular storng-acid cation exchange resin removing acetic acid.By ion exchange technique, its active site is occupied by silver or mercury, can be used for removing the iodide in the acetic acid.Relevant improvement patent also has US 5,227,524, and EP 0 282 787, and US 5,227,524, and WO 00/2779, and US 5,344,976, US5, and 801,279, US 5,139,981, and EP 0 882 508, EP 0 893 160 etc.Because of the resin price costliness of using, instability under acid and high temperature, easily swelling and deadly defect such as can not regenerate in acetic acid, and its application is restricted.
U.S. Pat 5,692, the silver-colored type molecular sieve that 735 modenites of having found to have 12 Yuans oxygen ring macroporous structures are the earliest made by exchange can be used for removing the iodide in the acetic acid.U.S. Pat 6,380,428 propose to make argentiferous type zeolite adsorbents, to be used for the removing of Korrosionsmedium iodide by exchange with LZ-210 zeolites (a kind of dealuminzation overstable gamma zeolite has 12 Yuans oxygen annular spaces of macropore road structure, aperture 0.71 nanometer).The ZSM-5 zeolite with 10 oxygen ring central hole structures (aperture 0.51X0.55,0.53X0.56 nanometer) that Taiwan patent 393464 has proposed silver-colored exchange can be used for the removing of iodide in the acetic acid.Chinese patent ZL 03141604.7 and ZL 03141605.5 introduce a kind of respectively with natural STI type zeolite with high silver carrying deiodination adsorbent of low silica ZSM-5 zeolite preparation and preparation method thereof respectively.These two kinds of used zeolites of adsorbent are 10 oxygen membered ring's mesoporous molecular sieves.Their silver carrying amount is higher, and in actual use, though it is better to take off the iodine effect, its granule strength is lower, and easy breaking and Dusting when using in acetic acid for a long time reduces its actual life.Chinese patent ZL200510025509.2 has then overcome above weakness and has developed the novel high-strength deiodination adsorbent.This adsorbent is compounded with STI zeolite and two kinds of molecular sieves of ZSM-5 zeolite with central hole structure.Its intensity is significantly increased.
But because single with the used zeolite cavity structure of above-mentioned silver molecular sieve deiodination adsorbent, not of uniform size for contained molecular dimension in the acetic acid, the iodide removal effect that complicated component is formed is relatively poor.Tracing it to its cause is, the intracrystalline hole diffusional resistance of large pore zeolite is little, help removing larger-size organic iodine molecule by physical absorption, but inorganic molecule iodine and the iodine less to size, its molecular motion is violent, and the sorptive power of large pore zeolite descends.And in the mesopore zeolite, the bigger organic iodate of molecular dimension since in the duct diffusion hindered, it is relatively poor to take off the iodine effect, and very easily be subjected to the influence of raw material content of iodine fluctuation of concentration and the process conditions such as variation by adsorbent bed hourly space velocity, operating temperature, taking off the iodine effect changes greatly, make that taking off the total content of iodine of iodine acetate products can't guarantee to be lower than 5ppb, sometimes even can surpass 10ppb.If the unsettled product acetic acid of this quality is used for synthesizing vinyl acetate, will make used noble metal catalyst slow poisoning, shorten its service life, cause heavy losses.
The present invention is directed to the weakness that the used zeolite molecular sieve of above patent is exposed in taking off iodine technology, invented and a kind ofly have two dimension 12 Yuans annular distance road openings, apertures and be respectively high silver carrying acetic acid deiodination adsorbent that the zeolite molecular sieve of 0.66X0.71 nanometer and 0.56X0.56 nanometer prepares and preparation method thereof.This new adsorbent is to the organic iodide of different molecular size and inorganic iodide, all have a good removal effect.Be enough to guarantee in the acetic acid after this adsorbent takes off iodinate that total content of iodine is lower than 5ppb.
Summary of the invention
The object of the present invention is to provide that a kind of to take off iodine effective, long service life be used for the carboxylated synthesis of carboxylic acid or carboxylic acid anhydrides technology is removed deiodination adsorbent of trace iodide and preparation method thereof.
The cation exchange capacity of zeolite is determined by the framework silicon-aluminum mol ratio.Silica alumina ratio is low more, and its cation exchange capacity (CEC) is also high more.And normally carrying out ion-exchange by the solubility salt solution that contains Ag with zeolite, the argentiferous deiodination adsorbent become silver ion type zeolite to make.Its principle of taking off iodine is that this tradable silver ion that is loaded on the zeolite dissociates out from zeolite, interact with the organic or inorganic iodine in the acetic acid, generate the AgI of indissoluble and remove, also there are stronger suction-operated in deiodination adsorbent carrier zeolite molecular sieve and organic iodide simultaneously, the huge lip-deep chemical group of zeolite can also and effect such as iodide generation complexing, under the acting in conjunction of above number of ways, can reach the good iodine effect of taking off.Therefore, take off iodine efficient (always taking off iodine amount and clearance etc.) and silver carrying amount and character such as zeolite structured is closely related.Wherein, silver carrying amount is high and low depends on zeolite structured silica alumina ratio.
Be used for the material that takes off iodine from the very strong carboxylic acid of acidity or carboxylic acid anhydrides, high structure and chemical stability must be arranged in acid, could satisfy the requirement of using.And usually low silica-alumina ratio A zeolite, X zeolite, Y zeolite, structure is very easily destroyed in acetic acid, and needing to improve framework si-al ratio through specially treated could use.The structure silica alumina ratio is greater than 5 modenite, dealuminzation FAU zeolite (LZ-210), ZSM-5 zeolite, FER zeolite, STI, HEU, BEA zeolite etc. has higher acidproof structural stability, and certain silver carrying amount is also arranged, and is the good base material of preparation deiodination adsorbent.
The high silver supported zeolite molecular sieve acetate deiodinase adsorber that the present invention proposes, be to have a sodium type BEA zeolite molecular sieve powder that two-dimentional 12 oxygen membered ring duct openings, aperture are respectively 0.66X0.71 nanometer and 0.56X0.56 nanometer, silica alumina ratio 5-25 with commercial, behind amorphous silicon aluminium binding agent mixed-forming, home position strengthening produces chemical bonding in handling under hydrothermal condition, carries out ion-exchange with silver salt solution again and carries silver and make.The adsorbent silver carrying amount is 7-24wt%.
This zeolite has the zeolite structured principal character X ray diffracting characteristic spectral line of BEA type:
| The feature diffracted ray | The 2 θ angles of diffraction (°) | Interplanar distance (nm) | Intensity |
| 1 (broad peak) | ??7.0-8.0 | ??1.63-1.11 | The strongest |
| The feature diffracted ray | The 2 θ angles of diffraction (°) | Interplanar distance (nm) | Intensity |
| ??2 | ??14.4 | ??0.616 | A little less than |
| ??3 | ??21.1 | ??0.422 | A little less than |
| ??4 | ??22.2 | ??0.402 | Very strong |
| ??5 | ??25.1 | ??0.356 | A little less than |
The preparation side of the composite zeolite deioidining adsorbent that the present invention proposes, concrete steps are as follows:
1. above-mentioned sodium type BEA zeolite molecular sieve powder was refluxed 1～5 hour at 80～120 ℃ with 0.5～2mol/l ammonium salt aqueous solution, exchange 3-4 time, alkali in the raw material or alkaline earth metal cation are removed; Use 0.05～1mol/l acetic acid again, be heated to 80～120 ℃ and refluxed 1～2 hour, exchange 2-3 time, or, obtain H type BEA zeolite 400～600 ℃ of following roastings 1～4 hour;
2. with above-mentioned H type BEA zeolite, being binding agent with Ludox, Alusil, white carbon, silica gel, waterglass, metakaolin or sodium-based montmorillonite, is strip or spherical particle by extrusion or roller forming, and binding agent accounts for the 15-30% of H type BEA zeolite quality;
3. with this strip or spherical particle, in pressure reaction still under 120-200 ℃ of temperature, be medium with water or steam, handled 5-48 hour through the hydro-thermal in-situ transesterification is brilliant, obtain the high strength substrate adsorbent;
4. above substrate adsorbent is taken off sodium with inorganic acid or ammonium salt solution and obtain H type BEA zeolite base adsorbent.The concentration of acid or ammonium salt is 0.1-6.0mol/L, and treatment temperature is 50-100 ℃, and the time is 5-24 hour.
With this substrate adsorbent in silver nitrate or silver acetate solution, under room temperature to 110 ℃ temperature the exchange 5-24 hour, can make BEA type zeolite deioidining adsorbent.
In the above-mentioned steps 1, used ammonium salt can be the one of the following kind: as NH
4Cl, NH
4NO
3, (NH
4)
2SO
4, NH
4Ac etc.
In the above-mentioned steps 4, all inorganic acids can be one of the following kind: HNO
3, HCl, H
2SO
4, NH
4Ac etc.; Inorganic ammonium salt can be one of the following kind: NH
4Cl, NH
4NO
3, (NH
4)
2SO
4, NH
4AC etc., its concentration is the 0.1-6.0 mole, and treatment temperature is 50-100 ℃, and the processing time is 5-24 hour; Container handling is tank reactor or cylindricality reaction bed.
In the above-mentioned steps 5, used silver nitrate or silver acetate solution concentration can be 0.01-1.0mol/l.
The acetic acid deiodination adsorbent silver carrying amount of the inventive method preparation is 7-24wt%.
Above-mentioned deiodination adsorbent can be applicable to carboxylic acid or the carboxylic acid anhydrides medium that carbonylation is synthetic, as acetic acid, aceticanhydride, propionic acid etc.
The compound deiodination adsorbent that is made by the present invention has crystallization degree height, big, the silver carrying amount advantages of higher of granule strength, can effectively remove organic iodide, inorganic iodide and molecular iodine in the carboxylated sintetics.
The specific embodiment
Embodiment 1:
The former powder of commercial zeolite group mineral carries out cation exchange according to the following steps and makes the H-STI zeolite:
1.BEA former powder joins in the 1.5mol/l ammonium chloride solution, solid-to-liquid ratio is 1: 8, is heated to 95～105 ℃ and refluxes 4 hours, exchanges the washing oven dry three times.
2. the BEA powder after ammonium chloride being exchanged promptly changes h-type zeolite into 550 ℃ of following roastings 5 hours.
3. the h-type zeolite after the roasting is added in the 1mol/l acetic acid, and solid-to-liquid ratio is 1: 6, and be heated to 90～95 ℃ and refluxed 4 hours, the washing oven dry, acquisition is used to prepare the H-BEA powder of deiodination adsorbent.
Embodiment 2:
H-BEA powder and adhesive silicon sol (SiO
2Content 20wt%) mixes, in bowling machine, make the bead of 1 millimeter of diameter.SiO in amount of zeolite in the bead and the binding agent
2Mass ratio be 80/20.X-ray powder diffraction shows relative crystallinity 80%.This bead heats in the closed stainless steel reactor and carries out the hydro-thermal intensive treatment, temperature 180 degree, 24 hours time.Make the bead of substrate adsorbent after the processing, relative crystallinity brings up to 105%, and intensity reaches 30 newton/grains, specific area 415m
2/ g.
Embodiment 3:
H-BEA powder and binding agent white carbon (SiO
2Content 25wt%) mixes, in bowling machine, make the bead of 1.5 millimeters of diameters.SiO in amount of zeolite in the bead and the binding agent
2Mass ratio be 75/25.X-ray powder diffraction shows relative crystallinity 78%.This bead heats in the closed stainless steel reactor and carries out the hydro-thermal intensive treatment, temperature 160 degree, 20 hours time.Make the bead of substrate adsorbent after the processing, relative crystallinity brings up to 103%, and intensity reaches 28 newton/grains, specific area 410m
2/ g.
Embodiment 4:
H-BEA powder and binding agent kaolin (SiO
2Content 30wt%) mixes, in bowling machine, make the cylindrical particle of 1 millimeter of diameter.SiO in amount of zeolite in the bead and the binding agent
2Mass ratio be 70/30.X-ray powder diffraction shows relative crystallinity 75%.This bead heats in the closed stainless steel reactor and carries out the hydro-thermal intensive treatment, temperature 200 degree, 40 hours time.Make the bead of substrate adsorbent after the processing, relative crystallinity brings up to 106%, and intensity reaches 35 newton/grains, specific area 419m
2/ g.
Embodiment 5:
The coccoid composite substrate adsorbent of embodiment 2 preparations, temperature is 80 ℃ on ion exchange column, carries out ion-exchange with the 0.05mol/l silver nitrate, Gu liquid /=15/1,10 hours time.Product is analyzed its silver carrying amount with X-ray fluorescence spectra (XRF) after washing, oven dry be 19.8%.
Embodiment 6:
The coccoid composite substrate adsorbent of embodiment 3 preparations, temperature is 90 ℃ on ion exchange column, carries out ion-exchange with the 0.05mol/l silver nitrate, Gu liquid /=20/1,15 hours time.Product is analyzed its silver carrying amount with X-ray fluorescence spectra (XRF) after washing, oven dry be 20.6%.
Embodiment 7:
The column composite substrate adsorbent of embodiment 4 preparations, temperature is 85 ℃ on ion exchange column, carries out ion-exchange with the 0.05mol/l silver nitrate, Gu liquid /=15/1,10 hours time.Product is analyzed its silver carrying amount with X-ray fluorescence spectra (XRF) after washing, oven dry be 14.6%.
Embodiment 20:
Carry out acetic acid with the deiodination adsorbent of embodiment 15 preparation and take off the iodine experiment: total content of iodine 50ppb (methyl iodide 22ppb+ iodide ion 28ppb) in the raw material acetic acid, the iodine effect is taken off in test under normal pressure and different temperatures, different air speed respectively, and the result is as follows.
40℃
| Air speed (hr -1) | ??2 | ??4 | ??6 | ??8 | ??10 |
| Methyl iodide content (ppb) in the tail washings | ??1.9 | ??2.1 | ??2.3 | ??2.7 | ??3.1 |
| Iodide ion content in the tail washings (ppb) | ??2.1 | ??2.3 | ??2.5 | ??2.9 | ??2.9 |
| Total content of iodine (ppb) in the tail washings | ??4.0 | ??4.4 | ??4.8 | ??5.8 | ??6.0 |
60℃
| Air speed (hr -1) | ??2 | ??4 | ??6 | ??8 | ??10 |
| Methyl iodide content (ppb) in the tail washings | ??1.3 | ??1.4 | ??1.6 | ??1.9 | ??2.3 |
| Air speed (hr -1) | ??2 | ??4 | ??6 | ??8 | ??10 |
| Iodide ion content in the tail washings (ppb) | ??1.8 | ??1.9 | ??2.4 | ??2.6 | ??2.8 |
| Total content of iodine (ppb) in the tail washings | ??3.1 | ??3.3 | ??4.0 | ??4.5 | ??5.1 |
Embodiment 21:
Carry out aceticanhydride with the deiodination adsorbent of embodiment 15 preparation and take off the iodine experiment; Concentrationofmethyiodide iodide is 50ppb in the raw material aceticanhydride, 60 ℃ of temperature, and experimental result is as follows:
| Air speed (hr -1) | ??2 | ??4 | ??6 | ??8 | ??10 |
| Methyl iodide content (ppb) in the tail washings | ??2.3 | ??2.7 | ??3.0 | ??3.5 | ??3.9 |
Embodiment 22:
Carry out acetic acid with the deiodination adsorbent of embodiment 18 preparation and take off the iodine experiment; Total iodo quantity 100ppb in the raw material acetic acid (methyl iodide 30ppb, ethyl iodide 35ppb, iodide ion 35ppb), 60 ℃ of temperature, experimental result is as follows:
| Air speed (hr -1) | ??2 | ??4 | ??6 | ??8 | ??10 |
| Methyl iodide content (ppb) in the tail washings | ??1.6 | ??1.8 | ??2.2 | ??2.6 | ??3.0 |
| Ethyl iodide content (ppb) in the tail washings | ??1.6 | ??1.9 | ??2.1 | ??2.4 | ??2.5 |
| Iodide ion content in the tail washings (ppb) | ??1.2 | ??1.5 | ??2.0 | ??2.3 | ??2.6 |
| Total content of iodine (ppb) in the tail washings | ??4.4 | ??5.2 | ??6.3 | ??7.3 | ??8.1 |
Claims (9)
1. high silver supported zeolite molecular sieve acetate deiodinase adsorber, it is characterized in that to have two-dimentional 12 oxygen membered ring's aperture structure zeolite molecular sieve powder, use the binding agent moulding, original position hydro-thermal intensive treatment produces chemical bond, makes after sodium, year silver are taken off in silver salt solution ion-exchange again; The adsorbent silver carrying amount is 7-24wt%.
2. high silver carrying zeolite acetic acid deiodination adsorbent according to claim 1 is characterized in that described two-dimentional 12 oxygen membered rings' duct, and its opening size is respectively 0.66X0.71 nanometer and 0.56X0.56 nanometer.
3. the preparation method of a high silver carrying zeolite acetic acid deiodination adsorbent is characterized in that concrete steps are as follows:
1) the sodium type BEA zeolite molecular sieve powder with two-dimentional ten dioxy person's annular distance road openings is added hot reflux with ammonium salt aqueous solution, exchange; Use acetic acid again, add hot reflux, exchange, or roasting obtain H type BEA zeolite;
2) with above-mentioned H type BEA zeolite, be shaped to strip or spherical particle with binding agent, the binding agent consumption is the 15-30% of H type BEA zeolite quality;
3), in pressure reaction still,, obtain the high strength substrate adsorbent through the brilliant processing of hydro-thermal in-situ transesterification with above-mentioned strip or spherical particle;
4) above substrate adsorbent is taken off sodium with inorganic acid or ammonium salt solution and obtain H type BEA zeolite base adsorbent;
5) with this substrate adsorbent in silver nitrate or silver acetate solution, add heat exchange, make BEA type zeolite deioidining adsorbent.
4. preparation method according to claim 3 is characterized in that described sodium type BEA zeolite powder aperture is respectively 0.66X0.71 nanometer and 0.56X0.56 nanometer, and silica alumina ratio is 5-25;
5. preparation method according to claim 3 is characterized in that described binding agent is Ludox, Alusil, white carbon, silica gel, waterglass, metakaolin or sodium-based montmorillonite.
6. preparation method according to claim 3 is characterized in that brilliant processing of described hydro-thermal in-situ transesterification is to be medium with water or steam, and treatment temperature is 120-200 ℃, processing time 5-48 hour.
7. preparation method according to claim 3 is characterized in that described inorganic acid is HNO
3, HCl, H
2SO
4Or NH
4Ac; Inorganic ammonium salt is NH
4Cl, NH
4NO
3, (NH
4)
2SO
4Or NH
4AC; Its concentration is the 0.1-6.0 mole, and treatment temperature is 50-100 ℃, and the processing time is 5-24 hour; Container handling is tank reactor or cylindricality reaction bed.
8. preparation method according to claim 3 is characterized in that described silver acetate or liquor argenti nitratis ophthalmicus concentration are 0.01-1.0mol/l.
9. preparation method according to claim 3 is characterized in that the acetic acid deiodination adsorbent silver carrying amount for preparing is 7-24wt%.
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| CN113019314A (en) * | 2021-03-03 | 2021-06-25 | 中国船舶重工集团公司第七一八研究所 | Methyl iodide adsorbent and preparation method thereof |
| CN113265703A (en) * | 2021-04-28 | 2021-08-17 | 中南大学 | Method for deiodinating metal arsenic crystal |
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