CN103204519A - Synthetic method of rare-earth silicon-aluminum molecular sieve - Google Patents
Synthetic method of rare-earth silicon-aluminum molecular sieve Download PDFInfo
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- CN103204519A CN103204519A CN2013101290952A CN201310129095A CN103204519A CN 103204519 A CN103204519 A CN 103204519A CN 2013101290952 A CN2013101290952 A CN 2013101290952A CN 201310129095 A CN201310129095 A CN 201310129095A CN 103204519 A CN103204519 A CN 103204519A
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Abstract
The invention discloses and provides a synthetic method of a rare-earth silicon-aluminum molecular sieve, which is simple in production process, short in process flow, high in production efficiency, lower in production cost and green and environment-friendly. In the synthetic method, a crystal compound of rare-earth silicon, a compound of aluminum, pure water, inorganic acid or inorganic base and guiding agent are used as initial materials, wherein the molar ratio of the primary initial materials is as follows: RE2O3/SIO2=0.25-3, SIO2/AL2O3 bigger than or equal to 5 and RE2O3/AL2O3=1-20; the adding amount of the guiding agent is 1%-15% of the material silicon oxide; and the reaction initial material mixture is stewed and crystallized for 20-48 hours under the temperature of 100-200 DEG C after being uniformly mixed. The synthetic method of the rear-earth silicon-aluminum molecular sieve can be used for directly replacing sodium ion by all or most of rare-earth ions, so that no or a little sodium ion is participated in the full production process of the rare-earth molecular sieve. The synthetic method of the rare-earth silicon-aluminum molecular sieve can be extensively applied to the molecular sieve field.
Description
Technical field
The present invention relates to a kind of synthetic method of rare earth silicon aluminum molecular screen.
Background technology
The Re-Y molecular sieve claims rare earth containing zeolite again, is a kind of pale yellow powder, is dissolved in strong acid and highly basic, and water insoluble and organic solvent is mainly used in the petroleum catalytic cracking catalysts.At present, China Patent No. is the preparation method that 91101221.4 " a kind of preparation method of rare-earth Y molecular sieve " discloses a kind of rare earth containing zeolite, and this method is with NaY molecular sieve and RE
3After in the aqueous solution, carrying out the primary ions exchange, the steps include: that (1) is with SiO
2/ Al
2O
3〉=4.8 NaY molecular sieve and concentration are that the mixed chlorinated rare earth aqueous solution of 0.5 ~ 5.0% weight ratio is according to NaY:RECl
3The weight ratio of=1:0.2 ~ 0.4 is at 60 ~ 100 ℃ of following ion-exchanges 0.3 ~ 2.0 hour, RECl
3It is 3.0 ~ 5.0 that the pH value of solution should be controlled at the PH that makes NaY mix rear slurry with it; (2) filter cake after the filtration washes with the deionized water of 20 times of own wts; (3) roasting: begin to feed the water vapor of weight space velocity 0.5 ~ 4.0 o'clock when being warming up to 200C, keep 450 ~ 600 ℃ of roastings of this flowing water steam atmosphere 1 ~ 3 hour.Actual Production Flow Chart is: (1) water glass+sodium aluminate synthesizes the NaY molecular sieve; (2) add the chlorination rare earth, carry out the RE first time
3 +With Na
+Ion-exchange, (3) washing is owing to need to remove a large amount of Na
+, therefore, use the rare-earth salts pickling usually; (4) high temperature sintering is separated out the sodium ion in the crystal; (5) for fully improving the put rate of rare earth on crystalline framework, carry out secondary RE again
3+ with Na+ ion-exchange; (6) filter washing again, to satisfy Na in the molecular sieve
2The requirement of O≤1.5%.
Therefore there is following shortcoming in above-mentioned technology: 1, the sodium ion that comes out after the rare earth ion exchanged first time need be washed except sodium greater than 20 times of water of xln; 2, since the part sodium ion in crystalline structure, need sodium ion could be separated out by the method for roasting, so need high-temperature roasting; 3, also need to dissolve the secondary exchange of carrying out rare earth ion and sodium ion; 4, also need washing.Therefore, the repeatedly loss of the rare earth that causes of washing reduces the yield of rare earth, and repeatedly a large amount of waste water of causing of washing bring great difficulty to wastewater treatment, simultaneously, with sodium ion because of the Na of product requirement more than 99.5%
+Get off with rare earth ion conversion, production process is difficulty relatively, needs long technical process, and for removing Na in the molecular sieve
+Increase very big cost, and brought the big pollution of tool to production environment.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides that a kind of production process is simple, technical process is short, production efficiency is high, production cost is lower and the synthetic method of the rare earth silicon aluminum molecular screen of environmental protection.
The technical solution adopted in the present invention is: the synthetic method of rare earth silicon aluminum molecular screen of the present invention is initial feed with the brilliant compound of rare earth silicon, compound, pure water, mineral acid or mineral alkali and the directed agents of aluminium;
Wherein, the mole proportioning of described main initial feed is: RE
2O
3/ SIO
2=0.25～3; SIO
2/ AL
2O
3〉=5; RE
2O
3/ AL
2O
3=1～20, the add-on of described directed agents is 1%～15% of raw material silicon oxide;
Reaction initial feed mixture mixes back static crystallization 20 ∽ 48 hours under the condition of 100～200 ° of temperature.
Further, the brilliant compound of described rare earth silicon is the xln with rare earth element and element silicon, at least a as in rare earth silicon metal, silicic acid rare earth, rare earth silica gel, the metasilicic acid rare earth.
Further, the compound of described aluminium is at least a in aluminum chloride, Tai-Ace S 150, aluminium hydroxide, pure aluminium silicate, metasilicic acid aluminium, sodium metaaluminate, the high sodium metaaluminate.
Further, the rare earth in the brilliant compound of described rare earth silicon is the mixture of rare earth single-element or multiple rare earth element.
Further, described directed agents is described rare earth silicon aluminum molecular screen, and the product of producing adds the effect that the part original product plays guiding as required.
Further, the potential of hydrogen of described mineral acid or described mineral alkali regulation system, described mineral alkali is at least a in sodium hydroxide or the potassium hydroxide, described mineral acid is at least a in sulfuric acid, hydrochloric acid, nitric acid, the pure aluminium silicate.
The invention has the beneficial effects as follows: because the synthetic method of rare earth silicon aluminum molecular screen of the present invention is initial feed with the brilliant compound of rare earth silicon, compound, pure water, mineral acid or mineral alkali and the directed agents of aluminium; Wherein, the mole proportioning of described main initial feed is: RE
2O
3/ SIO
2=0.25～3; SIO
2/ AL
2O
3〉=5; RE
2O
3/ AL
2O
3=1～20, the add-on of described directed agents is 1%～15% of raw material silicon oxide; Reaction initial feed mixture mixes back static crystallization 20 ∽ 48 hours under the condition of 100～200 ° of temperature.Compared with prior art, the present invention is with the whole or most of sodium ions that directly replace of rare earth ion, rare earth containing zeolite does not have in the production whole process or a spot of sodium ion participates in, can have following characteristics: 1, the present invention does not need once exchanging with secondary of rare earth ion and sodium ion in process of production; 2, the present invention in process of production, do not have roasting and repeatedly the washing program; 3, the present invention can once be synthesized to 40% with the content of rare earth silicon aluminum molecular screen middle-weight rare earths oxide compound, improved the content of rare earth containing zeolite middle-weight rare earths oxide compound greatly, and prior art just can reach 16% by the secondary rare earth exchanged; 4, because the rare earth oxide content height, improved rare earth containing zeolite greatly when producing catalyzer and kaolinic ratio.So production process of the present invention is simple, technical process is short, production efficiency is high, production cost is lower and environmental protection.
Embodiment
Below in conjunction with specific embodiment the present invention is further detailed, but is not limitation of the invention.
Embodiment one:
Raw material:
I. solid silicon acid rare earth (rare earth element is with lanthanum, cerium or lanthanum cerium mixture): 850KG;
Ii. Tai-Ace S 150 (containing 18 molecular crystal water, anhydrous slufuric acid aluminium content 51.3%): 290KG;
Iii. sodium hydroxide: 105KG;
Iv. pure water: 2000KG;
V. directed agents: 50KG;
The mole of main raw material consists of: RE
2O
3/ SIO
2=1.60; SIO
2/ AL
2O
3=7.30; RE
2O
3/ AL
2O
3=11.68, the add-on of described directed agents is 15% of siliconoxide mass;
Specified operational procedure is: under condition of stirring, add successively in the reactor after Tai-Ace S 150,30% pure water (about 600KG), sodium hydroxide stirs, add again and seal after 70% pure water, directed agents, silicic acid rare earth mix raw material, mixture is heated indirectly to 160 ℃, and constant temperature also made under the mixture static state crystallization 32 hours.Cooling, solid-liquid separation, pure water washing, drying obtain rare earth silicon aluminum molecular screen product.Be 38% through record total amount of rare earth with the rare earth weighting method.
Embodiment two:
Raw material:
I. solid silicon acid rare earth (rare earth element is with lanthanum, cerium or lanthanum cerium mixture): 900KG;
Ii. Tai-Ace S 150 (containing 18 molecular crystal water, anhydrous slufuric acid aluminium content 51.3%): 50KG;
Iii. pure aluminium silicate: 150KG;
Iv. pure water: 2000KG;
V. directed agents: 62KG;
The mole of main raw material consists of: RE
2O
3/ SIO
2=1.33; SIO
2/ AL
2O
3=6.02; RE
2O
3/ AL
2O
3=8.00, the add-on of described directed agents is 15% of siliconoxide mass;
Specified operational procedure is: under condition of stirring, adding pure aluminium silicate, 10% pure water (about 200KG), Tai-Ace S 150 in the reactor successively stirs, add again and seal after 70% pure water, silicic acid rare earth, directed agents mix raw material, mixture is heated indirectly to 160 ℃, and constant temperature also made under the mixture static state crystallization 32 hours.Cooling, solid-liquid separation, pure water washing, drying obtain rare earth silicon aluminum molecular screen product.Be 40% through record total amount of rare earth with the rare earth weighting method.
Compare with documents by two above-mentioned embodiment, total amount of rare earth is brought up to about 40% from 18%, is greatly improved.
The present invention can be widely used in the molecular sieve field.
Claims (6)
1. the synthetic method of a rare earth silicon aluminum molecular screen, it is characterized in that: present method is initial feed with the brilliant compound of rare earth silicon, compound, pure water, mineral acid or mineral alkali and the directed agents of aluminium;
Wherein, the mole proportioning of described main initial feed is: RE
2O
3/ SIO
2=0.25～3; SIO
2/ AL
2O
3〉=5; RE
2O
3/ AL
2O
3=1～20, the add-on of described directed agents is 1%～15% of raw material silicon oxide;
Reaction initial feed mixture mixes back static crystallization 20 ∽ 48 hours under the condition of 100～200 ° of temperature.
2. the synthetic method of rare earth silicon aluminum molecular screen according to claim 1, it is characterized in that: the brilliant compound of described rare earth silicon is for the xln of rare earth element and element silicon, at least a as in rare earth silicon metal, silicic acid rare earth, rare earth silica gel, the metasilicic acid rare earth.
3. the synthetic method of rare earth silicon aluminum molecular screen according to claim 1 is characterized in that: the compound of described aluminium is at least a in aluminum chloride, Tai-Ace S 150, aluminium hydroxide, pure aluminium silicate, metasilicic acid aluminium, sodium metaaluminate, the high sodium metaaluminate.
4. the synthetic method of rare earth silicon aluminum molecular screen according to claim 1, it is characterized in that: the rare earth in the brilliant compound of described rare earth silicon is the mixture of rare earth single-element or multiple rare earth element.
5. the synthetic method of rare earth silicon aluminum molecular screen according to claim 1, it is characterized in that: described directed agents is described rare earth silicon aluminum molecular screen.
6. the synthetic method of rare earth silicon aluminum molecular screen according to claim 1, it is characterized in that: the potential of hydrogen of described mineral acid or described mineral alkali regulation system, described mineral alkali is at least a in sodium hydroxide or the potassium hydroxide, and described mineral acid is at least a in sulfuric acid, hydrochloric acid, nitric acid, the pure aluminium silicate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498777A (en) * | 2015-12-06 | 2016-04-20 | 苏州科环环保科技有限公司 | Preparation method of metal loaded catalyst with aluminum silicate as carrier |
| CN107709238A (en) * | 2015-06-29 | 2018-02-16 | 三井金属矿业株式会社 | Manufacture method, filter aid, filter method and the surface modification pearlite of surface modification pearlite |
Citations (5)
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|---|---|---|---|---|
| CN1052290A (en) * | 1989-11-30 | 1991-06-19 | 中国石油化工总公司石油化工科学研究院 | The five-membered ring structure high-silicon zeolite that contains rare earth reaches synthetic |
| CN1058382A (en) * | 1990-07-23 | 1992-02-05 | 中国石油化工总公司石油化工科学研究院 | The preparation method of high-Si zeolite containing rare-earth five-membered ring structure |
| US6761875B2 (en) * | 2001-09-05 | 2004-07-13 | Engelhard Corporation | Rare earth silicate molecular sieves |
| CN1951808A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Preparation method of beta zeolite containing rare earth |
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2013
- 2013-04-15 CN CN201310129095.2A patent/CN103204519B/en active Active
Patent Citations (5)
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| CN1052290A (en) * | 1989-11-30 | 1991-06-19 | 中国石油化工总公司石油化工科学研究院 | The five-membered ring structure high-silicon zeolite that contains rare earth reaches synthetic |
| CN1058382A (en) * | 1990-07-23 | 1992-02-05 | 中国石油化工总公司石油化工科学研究院 | The preparation method of high-Si zeolite containing rare-earth five-membered ring structure |
| US6761875B2 (en) * | 2001-09-05 | 2004-07-13 | Engelhard Corporation | Rare earth silicate molecular sieves |
| CN1951808A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Preparation method of beta zeolite containing rare earth |
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| Title |
|---|
| BING YAN等: "Hydrothermal synthesis, physical characterization and photoluminescence of homologous-SBA-15 fabricated with Eu3+", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709238A (en) * | 2015-06-29 | 2018-02-16 | 三井金属矿业株式会社 | Manufacture method, filter aid, filter method and the surface modification pearlite of surface modification pearlite |
| CN105498777A (en) * | 2015-12-06 | 2016-04-20 | 苏州科环环保科技有限公司 | Preparation method of metal loaded catalyst with aluminum silicate as carrier |
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| CN103204519B (en) | 2015-06-03 |
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