CN102139887A - Method for preparing 4A molecular sieve by oil shale waste residue - Google Patents
Method for preparing 4A molecular sieve by oil shale waste residue Download PDFInfo
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- CN102139887A CN102139887A CN 201110044998 CN201110044998A CN102139887A CN 102139887 A CN102139887 A CN 102139887A CN 201110044998 CN201110044998 CN 201110044998 CN 201110044998 A CN201110044998 A CN 201110044998A CN 102139887 A CN102139887 A CN 102139887A
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- Prior art keywords
- oil shale
- waste residue
- molecular sieve
- residues
- mol ratio
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Abstract
The invention discloses a method for preparing a 4A molecular sieve by oil shale waste residue. The method comprises steps of (1) breaking, (2) mixing, (3) calcining, (4) aging, (7) crystallizing, (8) filtering and the like. The invention relates to an alkalizing calcination method which aims at solving the problem that most of silicon in the oil shale waste residue exists in the quartz state, has lower activity and is difficult to react with liquid state alkali, can synthesize alkali and waste residue in a fusing state, thereby generating the 4A molecular sieve. The method can lead the oil shale to be fully utilized, increases the utilization rate of the oil shale, improves the economical efficiency, avoids the accumulation of a large number of waste residues while making waste residue profitable, and reduces the amount of occupied land and the environmental pollution. The method has simple technical process, small investment and low cost and is a promising comprehensive utilization industrialization method for oil shale waste residue fine chemical engineering.
Description
One, technical field
The present invention relates to a kind of method for preparing the 4A molecular sieve with oil shale residues.
Two, background technology
Along with the minimizing day by day of petroleum resources, some more and more come into one's own such as substitute energys such as resinous shale.The main mode of utilizing of the resinous shale energy is to refine shale oil.But because the ash content proportion reaches more than 80% in the resinous shale, can a large amount of oil shale residues of discharging behind the resinous shale refinery.With Fushun is example, about about 5,000,000 tons of the oil shale residues of annual discharging.A large amount of waste residues is deposited in the open-air atmosphere for a long time, experience precipitation, leaching, weathering and self-combustion, series of physical, chemical reaction can take place, produced a large amount of pollutents and outwards discharging, caused peripheral region air, soil, underground water severe contamination.Contain 50 ~ 70%SiO in the oil shale residues
2, 10 ~ 25%Al
2O
3SiO
2And Al
2O
3Summation accounts for more than 70% of composition, prepares the main raw material of 4A molecular sieve just, and utilize oil shale residues to prepare the 4A molecular sieve it is turned waste into wealth, be a kind of effective way.The 4A molecular sieve is a kind of alkali metal aluminosilicate, energy planar water, NH
3, H
2S, sulfurous gas, carbonic acid gas, C
2H
5OH, C
2H
6, C
2H
4Be not more than the molecule of 4A Deng critical diameter.The drying that is widely used in gas, liquid also can be used for the refining and purification of some gas or liquid, as producing of argon gas.
Three, summary of the invention
The purpose of this invention is to provide and a kind ofly prepare the method for 4A molecular sieve, adopt this method that oil shale residues is turned waste into wealth, thereby solve land occupation and problem of environmental pollution, better reach the purpose of resinous shale comprehensive utilization simultaneously with oil shale residues.
For achieving the above object, the technical solution used in the present invention is:
1. oil shale residues is crushed to 200 orders;
2. according to SiO
2/ Al
2O
3Mol ratio is 1-6:1, Na
2O/SiO
2Mol ratio is 2-6:1, oil shale residues, aluminum oxide powder and sodium hydroxide is mixed fragmentation;
3. with step 2. the gained compound 500 ℃-1100 ℃ temperature lower calcination 1-5 hour;
4. with step 3. the gained grog be crushed to 200 orders;
5. according to water/Na
2The O mol ratio is 25-75:1, with step 4. the gained grog add in the entry;
6. under 20 ℃ of-60 ℃ of temperature, ageing 5-36 hour;
7. elevated temperature to 60 is ℃-120 ℃, crystallization 6-16 hour;
8. filter and promptly get the 4A zeolite product.
The compound of above-mentioned steps in 3. is to calcine in retort furnace.
The present invention is a kind of alkali method for calcinating that adds, and is primarily aimed at that silicon exists with quartzy form mostly in the oil shale residues, and activity is lower, is difficult to the problem with liquid alkali reaction, alkali is synthesized with waste residue under molten state, thereby generate the 4A molecular sieve.Adopt this method that oil shale residues is fully used, improved utilization ratio, increased economic benefit, avoided the bulk deposition of waste residue when turning waste into wealth, reduced the appropriation of land amount, reduced environmental pollution.Present method technological process is simple, invests for a short time, and cost is low, is a kind of oil shale residues fine chemistry industry, comprehensive utilization industrialization method that has prospect.
Four, embodiment
Embodiment 1:
1. oil shale residues is crushed to 200 orders;
2. according to SiO
2/ Al
2O
3Mol ratio is 3:1, Na
2O/SiO
2Mol ratio is 4:1, oil shale residues, aluminum oxide powder and sodium hydroxide is mixed fragmentation;
3. with step 2. the gained compound put into retort furnace 750 ℃ of temperature lower calcinations 3 hours;
4. with step 3. the gained grog be crushed to 200 orders;
5. according to water/Na
2The O mol ratio is 60:1, with step 4. the gained grog add in the entry;
6. under 20 ℃ of temperature, ageing 10 hours;
7. elevated temperature to 100 ℃, crystallization 6 hours;
8. filter and promptly get the 4A zeolite product.
Embodiment 2:
1. oil shale residues is crushed to 200 orders;
2. according to SiO
2/ Al
2O
3Mol ratio is 2:1, Na
2O/SiO
2Mol ratio is 3:1, oil shale residues, aluminum oxide powder and sodium hydroxide is mixed fragmentation;
3. with step 2. the gained compound put into retort furnace 600 ℃ of temperature lower calcinations 2 hours;
4. with step 3. the gained grog be crushed to 200 orders;
5. according to water/Na
2The O mol ratio is 70:1, with step 4. the gained grog add in the entry;
6. under 60 ℃ of temperature, ageing 18 hours;
7. elevated temperature to 110 ℃, crystallization 16 hours;
8. filter and promptly get the 4A zeolite product.
The foregoing description gained molecular sieve is measured through X-ray diffraction, all meets the aperture requirement of 4A molecular sieve, and its Static Water suction rate can reach more than 20%, reaches standard HG/T 2524-93 requirement.
Claims (2)
1. one kind prepares the method for 4A molecular sieve with oil shale residues, comprises the steps:
1. oil shale residues is crushed to 200 orders;
2. according to SiO
2/ Al
2O
3Mol ratio is 1-6:1, Na
2O/SiO
2Mol ratio is 2-6:1, oil shale residues, aluminum oxide powder and sodium hydroxide is mixed fragmentation;
3. with step 2. the gained compound 500 ℃-1100 ℃ temperature lower calcination 1-5 hour;
4. with step 3. the gained grog be crushed to 200 orders;
5. according to water/Na
2The O mol ratio is 25-75:1, with step 4. the gained grog add in the entry;
6. under 20 ℃ of-60 ℃ of temperature, ageing 5-36 hour;
7. elevated temperature to 60 is ℃-120 ℃, crystallization 6-16 hour;
8. filter and promptly get the 4A zeolite product.
2. according to claim 1ly a kind ofly prepare the method for 4A molecular sieve with oil shale residues, it is characterized in that: the compound of described step in 3. is to calcine in retort furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110044998 CN102139887A (en) | 2011-02-25 | 2011-02-25 | Method for preparing 4A molecular sieve by oil shale waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110044998 CN102139887A (en) | 2011-02-25 | 2011-02-25 | Method for preparing 4A molecular sieve by oil shale waste residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102139887A true CN102139887A (en) | 2011-08-03 |
Family
ID=44407711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110044998 Pending CN102139887A (en) | 2011-02-25 | 2011-02-25 | Method for preparing 4A molecular sieve by oil shale waste residue |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291353A (en) * | 2013-07-20 | 2015-01-21 | 东北大学 | Method for preparation of 4A zeolite from lateritic nickel ore acid leaching residue |
| CN104291354A (en) * | 2013-07-20 | 2015-01-21 | 东北大学 | Method for preparation of zeolite 4A and vanadium-titanium catalyst from vanadium slag |
| CN106241829A (en) * | 2016-08-29 | 2016-12-21 | 中国矿业大学(北京) | A kind of oil shale waste prepares the method for faujasite |
-
2011
- 2011-02-25 CN CN 201110044998 patent/CN102139887A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 《Fuel》 20050609 Nadia Regina Camargo Fernandes Machado，et al Synthesis of Na-A and -X zeolites from oil shale ash 第2289－2294页 1-2 第84卷, * |
| 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 20091015 张红 以油页岩灰为原料合成沸石分子筛的研究 第37-40页 1-2 , 第10期 * |
| 《过程工程学报》 20081231 刘艳辉，等 油页岩渣制备沸石及其吸附Cr6+性能 第1108-1111页 1-2 第8卷, 第6期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291353A (en) * | 2013-07-20 | 2015-01-21 | 东北大学 | Method for preparation of 4A zeolite from lateritic nickel ore acid leaching residue |
| CN104291354A (en) * | 2013-07-20 | 2015-01-21 | 东北大学 | Method for preparation of zeolite 4A and vanadium-titanium catalyst from vanadium slag |
| CN104291353B (en) * | 2013-07-20 | 2016-07-06 | 东北大学 | A kind of method preparing 4A zeolite for raw material with lateritic nickel ore acid leaching residue |
| CN106241829A (en) * | 2016-08-29 | 2016-12-21 | 中国矿业大学(北京) | A kind of oil shale waste prepares the method for faujasite |
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Application publication date: 20110803 |