CN1327949C - High-strength composite zeolite deioidining adsorbent and its preparing method - Google Patents
High-strength composite zeolite deioidining adsorbent and its preparing method Download PDFInfo
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- CN1327949C CN1327949C CNB2005100255092A CN200510025509A CN1327949C CN 1327949 C CN1327949 C CN 1327949C CN B2005100255092 A CNB2005100255092 A CN B2005100255092A CN 200510025509 A CN200510025509 A CN 200510025509A CN 1327949 C CN1327949 C CN 1327949C
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- zeolite
- adsorbent
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Abstract
The present invention relates to a high-intensity composite deiodination adsorbent for removing iodides in the technology of combining carbonyl into a carboxylic acid or carboxylic anhydride product, and a preparation method of the high-intensity composite deiodination adsorbent. Natural mineral zeolite, namely stilbite (whose Chinese code is CXN, English code is STI and scientific name is stilbite) is made into H-STI through cation exchange. Then, the stilbite is mixed with an artificially synthesized commodity H-ZSM-5 zeolite and is formed by adding an adhesive. After the mixture is strengthened and is plated with silver, the adsorbent is prepared. The pellet intensity of the adsorbent with the diameter of 1 millimeter can reach 40 N/granule. The adsorbent can effectively remove organic iodides, inorganic iodides and molecule iodine in products combined from carbonyl.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of compound deiodination adsorbent that is used for synthetic carboxylic acid of carbonylation or carboxylic acid anhydrides product technology removal iodide 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 below the 10ppb.
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 5,692,735 have found the silver-colored type molecular sieve that modenite is made by exchange the earliest, 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 zeolite (a kind of sealumination modified Y zeolite).The ZSM-5 zeolite that Taiwan patent 393464 has proposed silver-colored exchange can be used for the removing of iodide in the acetic acid.
Chinese patent (application) CN 03 141604.7 and CN 03 141605.5 introduce respectively a kind of with natural STI type zeolite preparation and with high silver carrying deiodination adsorbent of ZSM-5 zeolite preparation and preparation method thereof.These two kinds of high silver carrying deiodination adsorbents in actual use, though it is effective to take off iodine, life expectancy is very long, because of the granule strength after its moulding is lower, easy breaking and Dusting when using in acetic acid for a long time reduces its actual life.
Compound deiodination adsorbent of novel high-strength that the present invention is directed to the weakness in the above-mentioned patent and develop and preparation method thereof.
Summary of the invention
The objective of the invention is to 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 high strength deiodination adsorbent of 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 rice from zeolite, interacts with organic or inorganic iodine in the acetic acid, generates the AgI of indissoluble and reaches the purpose of removing trace iodine.Therefore, it is closely related to take off iodine efficient (always taking off iodine amount and clearance etc.) and silver carrying amount.Depend on zeolite structured silica alumina ratio and silver carrying amount is high and low.
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 and can't use in acetic acid.The structure silica alumina ratio is greater than artificial synthetic zeolite and natural STI zeolites such as 5 modenite, sealumination modified Y zeolite (LZ-210), ZSM-5 zeolites, and they have higher acidproof structural stability, and certain silver carrying amount is also arranged.It is the good base material of preparation deiodination adsorbent.
The deiodination adsorbent that the present invention proposes, it is a kind of composite type zeolite deiodination adsorbent, it is made up of 2 kinds of zeolites, is promptly mixed after the binding agent that moulding is used produces chemical bonding and prepares in the hydro-thermal intensive treatment by Hydrogen natural zeolite H-STI zeolite and artificial synthetic H-ZSM-5 zeolite.Its crystallization degree obviously improves, and therefore its granule strength obviously strengthens.Wherein, the mass ratio of H-STI and H-ZSM-5 is 70: 30～85: 15, and binding agent and zeolite total mass ratio are 15: 85～25: 75, and load silver on the composite zeolite deioidining adsorbent.
High-strength composite zeolite deioidining adsorbent of the present invention has following architectural feature: have the aperture to be respectively ten oxygen membered ring ducts and 0.56 * 0.27nm, the eight oxygen membered ring ducts of 0.5 * 0.47nm, 0.56 * 0.53nm, 0.56 * 0.51nm in the skeleton.Its powder x-ray diffraction (XRD) spectrum has following principal character diffracted ray: d=10.9～11.3 (vs); 9.6～10.0 (vs); .9.0～9.2 (vs); 8.7～8.9 (ms); 7.8～8.1 (ms); 4.4～4.7 (ms); 4.2～4.3 (ms); 3.9～4.1 (vs); 3.7～3.9 (vs); 3.6～3.8 (ms); 3.2～3.4 (vs); 3.0～3.1 (ms).
The preparation method of the composite zeolite deioidining adsorbent that the present invention proposes is as follows:
1, the raw material natural STI zeolite 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 Hydrogen STI (H-STI) zeolite 400～600 ℃ of following roastings 1～4 hour;
2, above-mentioned H-STI zeolite being mixed with commercially available H-ZSM-5 zeolite, is binding agent with Ludox or amorphous silica or Alusil, is strip or spherical particle by extrusion or roller forming; Wherein, the mass ratio of H-STI and H-ZSM-5 is 70: 30～85: 15, and binding agent and zeolite total mass ratio are 15: 85～25: 75;
4, with this strip or spherical particle, in pressure reaction still under 60～300 ℃ of temperature, through hydrothermal treatment consists 10～120 hours, obtain high-intensity composite substrate adsorbent;
5, with this substrate adsorbent in silver nitrate or silver acetate solution, under room temperature to 110 ℃ temperature, exchange 5～24 hours, can make high-strength composite zeolite deioidining adsorbent.
In the above-mentioned steps (5), used silver nitrate or silver acetate solution concentration can be 0.01～1.0mol/L.
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.
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 deiodination adsorbent that is made by the present invention has very high taking off iodine efficient, very long service life.Diameter is that this adsorbent bead intensity of 1 millimeter can reach 40 newton/grains.Can effectively remove organic iodide, inorganic iodide and molecular iodine in the carboxylated sintetics.
Description of drawings
Fig. 1 is a sample powder X-ray diffraction spectrum before the intensive treatment.
Fig. 2 is a sample powder X-ray diffraction spectrum after the intensive treatment.
The specific embodiment
One of raw material that the present invention is used is natural zeolite the mineral----foresite of China's high yield, the called after STI of international zeolite association zeolite, and its structure cell chemical composition is Na
0.2Mg
0.1Ca
8.4" Al
17.2Si
54.8O
144" 65H
2O belongs to rich ca-form zeolite.This zeolite is a high-crystallinity pure phase stilbite type zeolite group mineral powder.Two of raw material is commercially available artificial synthetic H-ZSM-5 zeolite powders, and it is a kind of silica-rich zeolite.
Embodiment 1:
The former powder of STI mineral carries out cation exchange according to the following steps and makes the H-STI zeolite:
1.STI former powder joins in the 1.0mol/L ammonium chloride solution, solid-to-liquid ratio is 1: 10, is heated to 95～103 ℃ and refluxes 2 hours, exchanges the washing oven dry four times.
2. the STI powder after ammonium chloride being exchanged promptly changes h-type zeolite into 500 ℃ of following roastings 3 hours.
3. the h-type zeolite after the roasting is added in the 0.5mol/L acetic acid, and solid-to-liquid ratio is 1: 10, is heated to 95～100 ℃ and refluxes 2 hours, and the washing oven dry obtains the H-STI powder.
Embodiment 2:
The H-STI powder mixes with 70/30 ratio with the H-ZSM-5 powder, again with adhesive silicon sol (SiO
2Content 25wt%) mixes, in bowling machine, make the bead of 2 millimeters of diameters.SiO in amount of zeolite in the bead and the binding agent
2Mass ratio be 75/25.
The X-ray diffractogram of this bead is seen accompanying drawing 1.Its principal character reflects that the ratio of total clean intensity/total diffracted intensity of its crystalline material relative amount is 0.28.The average crushing strength of this bead is 18 newton/grains.
Embodiment 3:
The bead that is made by embodiment 2 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 composite substrate adsorbent after the processing, its X-ray diffractogram is seen accompanying drawing 2.The ratio that reflects total clean intensity/total diffracted intensity of its crystalline material relative amount is 0.38.Its principal character diffraction maximum d=10.9～11.3 (vs); 9.6～10.0 (vs); .9.0～9.2 (vs); 8.7～8.9 (ms); 7.8～8.1 (ms); 4.4～4.7 (ms); 4.2～4.3 (ms); 3.9～4.1 (vs); 3.7～3.9 (vs); 3.6～3.8 (ms); 3.2～3.4 (vs); 3.0～3.1 (ms).Contrast accompanying drawing 1 and 2, as can be seen, after the hydro-thermal intensive treatment, total relative amount of bead mesolite has improved 36%. the average crushing strengths of bead after intensive treatment and has improved 2.2 times before the processing, reaches 40 newton/grains.
Embodiment 4:
The H-STI powder mixes with 85/15 ratio with the H-ZSM-5 powder, mixes with binding agent Alusil (silica and aluminium oxide total content 52wt%) again, makes the column type particle of 2 millimeters of diameters in extrusion part machine.Silica is 85/15 with aluminium oxide quality ratio in amount of zeolite in the particle and the binding agent.The average crushing strength of this bead is 15 newton/grains.
Embodiment 5:
The particle that is made by embodiment 4 heats in the closed stainless steel reactor and carries out the hydro-thermal intensive treatment, temperature 120 degree, 5 days time.Bead after the processing, its X-ray diffraction have the principal character diffraction maximum identical with embodiment 3.The average crushing strength 28 newton/grains of the particle after intensive treatment.
Embodiment 6-8 is listed in the table below:
| Embodiment | The substrate raw material | The intensive treatment condition | Average grain intensity (newton/grain) | ||
| Temperature (℃) | Time (my god) | Before the processing | After the processing | ||
| 6 | Embodiment 2 beads | 150 | 4 | 18 | 35 |
| 7 | Embodiment 4 particles | 170 | 3 | 15 | 32 |
| 8 | Embodiment 4 particles | 110 | 5 | 15 | 25 |
Embodiment 9:
The coccoid composite substrate adsorbent of example 3 preparation, 60 ℃ of temperature are carried out ion-exchange with the 0.05mol/L silver nitrate on ion exchange column, Gu liquid /=13/1,10 hours time.Product is analyzed its silver content with EDX after washing, oven dry be 6.8%.
Embodiment 10:
The graininess composite substrate adsorbent of example 5 preparation, 80 ℃ of temperature are carried out ion-exchange with the 0.10mol/L silver acetate on ion exchange column, Gu liquid /=10/1,5 hours time.Product is analyzed its silver content with EDX after washing, oven dry be 10.0%.
Embodiment 11:
Carry out acetic acid with the compound deiodination adsorbent of reinforcement of embodiment 10 preparation and take off iodine test; Concentrationofmethyiodide iodide is 39.6ppb in the raw material acetic acid, does the adsorption effect experiment respectively under normal pressure and 40 ℃, 60 ℃ and different air speed.The result who obtains is as follows:
In the time of 40 ℃
| Air speed (hr -1) | 2 | ＜4 | 6 | 7 | 9 |
| Tail washings methyl iodide content mean value (ppb) | 5.98 | 4.77 | 6.33 | 6.875 | 6.33 |
In the time of 60 ℃
| Air speed (hr -1) | 3 | 5 | 7 | 9 | 12 |
| Tail washings methyl iodide content mean value (ppb) | 2.68 | 2.343 | 2.61 | 3.154 | 5.25 |
Embodiment 12:
Carry out acetic anhydride with the compound deiodination adsorbent of reinforcement of embodiment 10 preparation and take off iodine test; Concentrationofmethyiodide iodide is 47ppb in the raw acetic acid acid anhydride, the effect experiment of absorption in continuous 10 hours, and the result who obtains is as follows:
| Sample number into spectrum | Adsorption time (hr) | Adsorption column tail washings MeI concentration (ppb) | Air speed (/h) |
| 1 | 1 | 2.93 | 4.4 |
| 2 | 3 | 3.278 | 4.4 |
| 3 | 6 | 1.978 | 4.4 |
| 4 | 8 | 1.718 | 4.4 |
| 5 | 10 | 2.272 | 4.4 |
Claims (5)
1. a high-strength composite zeolite deioidining adsorbent is characterized in that being mixed after moulding produces chemical bonding with binding agent and prepares in the hydro-thermal intensive treatment with artificial synthetic Hydrogen silica-rich zeolite H-ZSM-5 zeolite by Hydrogen natural zeolite H-STI; Wherein, the mass ratio of H-STI and H-ZSM-5 is 70: 30～85: 15, and binding agent and zeolite total mass ratio are 15: 85～25: 75; And load silver on the composite zeolite deioidining adsorbent.
2. composite zeolite deioidining adsorbent according to claim 1 is characterized in that described binding agent is Ludox, Alusil or amorphous silica.
3. according to the preparation method of the described composite zeolite deioidining adsorbent of claim 1, it is characterized in that concrete steps are as follows:
(1) the raw material natural STI zeolite 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 times, or, obtain the H-STI zeolite 400～600 ℃ of following roastings 1～4 hour;
(2) above-mentioned H-STI zeolite being mixed with commercially available H-ZSM-5 zeolite, is binding agent with Ludox or amorphous silica or Alusil, is strip or spherical particle by extrusion or roller forming; Wherein, the mass ratio of H-STI and H-ZSM-5 is 70: 30～85: 15, and binding agent and zeolite total mass ratio are 15: 85～25: 75;
(3) with this strip or spherical particle, in pressure reaction still under 60～300 ℃ of temperature, through hydrothermal treatment consists 10～120 hours, obtain high-intensity composite substrate adsorbent;
(4) with this substrate adsorbent in silver nitrate or silver acetate solution, under room temperature to 110 ℃ temperature, exchange 5～24 hours, can make high-strength composite zeolite deioidining adsorbent.
4. preparation method according to claim 3 is characterized in that used ammonium salt is one of the following kind: NH
4Cl, NH
4NO
3, (NH
4)
2SO
4, NH
4AC.
5. preparation method according to claim 3, the concentration that it is characterized in that used silver acetate or liquor argenti nitratis ophthalmicus is 0.01～1.0mol/L.
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| CN1327949C true CN1327949C (en) | 2007-07-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811023A (en) * | 2010-03-11 | 2010-08-25 | 上海复旭分子筛有限公司 | Preparation method, product and applications thereof of acetate deep deiodination adsorbent |
| CN109399663A (en) * | 2018-09-04 | 2019-03-01 | 复榆(张家港)新材料科技有限公司 | The production method of ultra-fine NH4-STI powder |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| US6380428B1 (en) * | 1998-03-06 | 2002-04-30 | Uop Llc | Method for treating a liquid stream contaminated with an iodine-containing compound using a cation-exchanged zeolite |
| CN1478595A (en) * | 2003-07-10 | 2004-03-03 | 上海吴泾化工有限公司 | Preparation method of high silver carrying ZSM-5 zeolite deiodine adsorbing agent |
| CN1486784A (en) * | 2003-07-10 | 2004-04-07 | 复旦大学 | Zeolite deiodination adsorbent with high silver carrying amount and its prepn process |
| CN1586698A (en) * | 2004-07-13 | 2005-03-02 | 上海吴泾化工有限公司 | Method for removing iodine and iodine compound impurity |
-
2005
- 2005-04-28 CN CNB2005100255092A patent/CN1327949C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| US6380428B1 (en) * | 1998-03-06 | 2002-04-30 | Uop Llc | Method for treating a liquid stream contaminated with an iodine-containing compound using a cation-exchanged zeolite |
| CN1478595A (en) * | 2003-07-10 | 2004-03-03 | 上海吴泾化工有限公司 | Preparation method of high silver carrying ZSM-5 zeolite deiodine adsorbing agent |
| CN1486784A (en) * | 2003-07-10 | 2004-04-07 | 复旦大学 | Zeolite deiodination adsorbent with high silver carrying amount and its prepn process |
| CN1586698A (en) * | 2004-07-13 | 2005-03-02 | 上海吴泾化工有限公司 | Method for removing iodine and iodine compound impurity |
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