CN1093087C - Process for preparing high-crystallinity X-type zeolite from coal gangue as raw material - Google Patents
Process for preparing high-crystallinity X-type zeolite from coal gangue as raw material Download PDFInfo
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- CN1093087C CN1093087C CN00119586A CN00119586A CN1093087C CN 1093087 C CN1093087 C CN 1093087C CN 00119586 A CN00119586 A CN 00119586A CN 00119586 A CN00119586 A CN 00119586A CN 1093087 C CN1093087 C CN 1093087C
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- coal gangue
- type zeolite
- crystallinity
- deferrization
- coal
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Abstract
The present invention relates to a method for preparing X type zeolite with high crystallization degree by using coal gangue as raw material. The crystallization degree zeolite prepared in the prior art is limited since iron is not removed; in the present invention, an acidic iron removing agent is used for preprocessing to remove iron minerals in raw material in a leaching mode, and coal gangue which is processed by alkali fusion, activation and iron removal at high temperature is aged, crystallized in a hydrothermal mode, etc. to prepare X type zeolite with high crystallization degree. An XRD spectrogram indicates that the crystallization degree of the X type zeolite prepared by using the method of the present invention is more than 80%, the crystallization degree of the best X type zeolite prepared by using the method of the present invention reaches 90%, the crystallization degree of the X type zeolite prepared by using the method of the present invention is higher than that of the X type zeolite prepared by using coal gangue which is not processed by iron removal under the same preparation condition, and the whiteness of the product is greatly improved.
Description
The present invention be a kind of be the method for feedstock production high-crystallinity X-type zeolite with the coal gangue.
Coal gangue is the solid waste of rejecting in coal mining and the washing process, and major ingredient is the oxide compound and the residual carbon of silicon, aluminium, iron, calcium, magnesium etc.The produced quantity of coal gangue is very big, account for the 10--20% of raw coal output, most of collieries adopt the method for air storage to handle, and have have not only occupied tract, also cause serious environmental to pollute, therefore fully utilizing coal gangue is a problem that has economic benefit and social benefit concurrently.Country also attaches great importance to the coal gangue comprehensive utilization technique of encourage growth high-tech content and high added value to the comprehensive utilization work of coal gangue.
At present, the comprehensive utilization of coal gangue mainly comprises and utilizes residual carbon generating, preparation material of construction, extracts AlCl
3, TiO
2, SiO
2Deng approach such as industrial chemicals.But the not high or shortcomings such as raw material effective ingredient-use rate is low, running cost height of these development approach ubiquity economic value addeds.Therefore, utilize coal gangue, and to improve its utility value still be a problem demanding prompt solution how more profoundly.
Recently, it is raw material that Ni Zheng etc. have proposed with the coal gangue, by high temperature alkali fuse activation prepare X type zeolite method (Ni Zheng, Tang's chin or cheek, Hua Weiming, petrochemical complex 2000,29:336), for the approach that provides is provided for the high added value of coal gangue.But owing to contain a certain amount of iron mineral in most of coal gangues, in the crystallization process, the part iron atom has replaced the aluminium atom in the zeolite framework, reduced the degree of crystallinity of product, and because the existence of impurity iron, the whiteness of product also is affected, therefore, degree of crystallinity with the X type zeolite of the method for propositions such as Ni Zheng preparation is difficult to break through 80%, and the zeolite color is light yellow, makes the practical application of product be subjected to certain limitation.
The purpose of this invention is to provide a kind of method with bastard coal masonry feedstock production high-crystallinity X zeolite.
The used coal gangue raw material of the present invention can be various types of coal gangues, the promptly different places of production, and the coal gangue that composition differs also can be the mineral substance of carbon containings such as flyash, mud coal, volcanic ash and silico-aluminate.
The method for preparing the high-crystallinity X zeolite involved in the present invention is as follows:
1. the feed coal spoil is dipped in the acid deferrization liquid of finite concentration and temperature, stirs deferrization one regularly
Between;
2. after the deferrization, suction filtration is washed to neutrality;
3. after the oven dry of the product behind the suction filtration, the method for preparing X type zeolite by existing coal gangue is carried out, bag
Draw together high temperature alkali fuse, add steps such as water aging (adding or do not add crystal seed), hydrothermal crystallizing;
4. product suction filtration, the washing after the crystallization gets product after the drying.
Said raw material is that various types of coal gangues and other are the mineral of major ingredient, for example flyash, volcanic ash etc. with the silico-aluminate in 1; Said acid deferrization liquid is meant various acidic solutions, for example HCl, H
2SO
4, HNO
3, H
2C
2O
4Deng; The consumption of acid solution is with H in the acid solution
+Mole number and the ratio of coal gangue quality represent that its scope is 0.0005～0.1molH
+/ g coal gangue, promptly every gram coal gangue is with containing 0.0005～0.1molH
+Acid solution soak deferrization.The acidleach temperature can be 0-100 ℃; Leaching time can be 15-480min.
Deferrization acidic solution of the present invention can be HCl, H
2SO
4, HNO
3, H
2C
2O
4, these acid values are honest and clean to be easy to get, and its consumption is at 0.005～0.04molH
+/ g coal gangue is more suitable.
20-80 ℃ of acidleach temperature of the present invention is more suitable, and leaching time can be in 20-120min under this temperature, reaches the purpose that not only improves preparation efficiency but also guarantee preparation quality.
Said crystal seed can add also and can not add in 3, if add crystal seed, its add-on can be the 0-10% that is equivalent to the product of roasting quality.
Crystal seed add-on of the present invention is 0-5% preferably.
The invention provides with the coal gangue is the method for feedstock production high-crystallinity X-type zeolite, the method that this method and existing coal gangue prepare X type zeolite is compared and has been increased by a step deferrization step, the quality of product improves greatly, the X type zeolite of gained is than the high 10-20% of X type zeolite crystallinity of traditional method preparation, and the whiteness of product also is greatly improved, and is that the industrial mass production of feedstock production high quality X type zeolite becomes possibility thereby make with the coal gangue.
The zeolite that the inventive method makes is owing to improved degree of crystallinity, and product performance improve greatly, if make sorbent material, and catalyzer, ion-exchanger or siccative will obtain better effect than existing technical products.
Following table be the X type zeolite that makes of present method and existing method and commodity X zeolite part character relatively
| The relative crystallinity (%) of X type zeolite | Soaking of iron removes amount (gFe 2O 3/ g coal gangue) | Silica alumina ratio | |
| A 1 | 83 | 4.6 | 2.8 |
| A 2 | 85 | 3.3 | 2.7 |
| A 3 | 90 | 3.3 | 2.7 |
| B | 73 | Not deironing | 2.8 |
| C | 100 | 2.7 |
Fig. 1 is the X type zeolite A that present method makes
1And A
3XRD spectra
Fig. 2 is the X type zeolite A that present method makes
3SEM figure
Fig. 3 is A
3The high multiple SEM photo of sample
Following example is to further specifying that the X prepare zeolite method of high-crystallinity provided by the present invention is done.
Example 1
Getting 2g is crushed to tafelberg, 100 purpose Henan seven pit coal spoils (it basic composition is 4.56%C, 50.4%SiO
2, 22.5%Al
2O
3And all the other parts are the oxide compound of Ca, Mg, Fe, Mn etc.), press 0.02molH
+The ratio of/g coal gangue adds the HCl solution of 10ml 4mol/l, stirs 120min in 80 ℃ oil bath, solution after the suction filtration deferrization, and be washed to neutrality and (use AgNO
3Solution check Cl
-), after the oven dry of suction filtration product, press sodium silicon mol ratio Na
2O/SiO
2=1.3 add the NaOH strong solution of 8.736g 20% (wt%), mix in porcelain mortar, after the oven dry, mixture are ground and are transferred in the porcelain boat.Porcelain boat is placed tube furnace, roasting under air atmosphere.Earlier 120 ℃ of following roastings 1 hour, to eliminate planar water, the speed with 10 ℃/min was warming up to 850 ℃ then, and constant temperature 3 hours.After treating that the alkali fusion thing is cooled to room temperature, with its grinding powder and be transferred in the plastic test tube, add 15.6g distilled water and (make C
NaOH=2.8moll
-1), under the magnetic agitation condition, aged at room temperature 12 hours.Behind aging the finishing, reaction solution is transferred in the stainless steel cauldron 100 ℃ of crystallization 10 hours.Crystallization product after filtration, promptly get X type zeolite after the washing, drying.This product is designated as A
1
Example 2
Press example 1 described method and handle coal gangue, but press 0.005mol H
+The ratio of/g coal gangue adds the HCl solution of 10ml1mol/l, the acidleach temperature is respectively 40 ℃ and 80 ℃, leaching time is respectively 80min and 20min, and when aging, add the crystal seed (commodity X type zeolite) that is equivalent to product of roasting quality 4%, crystallization time was respectively 10 hours and 8 hours, and the product that makes is designated as A respectively
2, A
3
Comparative Examples 1
Coal gangue with not deironing prepares X type zeolite by traditional preparation method.This product is designated as B.
Comparative Examples 2
Commodity X type zeolite by Sinoamerican Joint Venture Jinzhong Molecular Sieves Co., Ltd., Shanghai's production.This product is designated as C.
Example 3
The deferrization liquid of above-mentioned portioned product is measured the deferrization rate with UV-VIS (carrying out) method on Shimazu UV-240 ultraviolet spectrophotometer, product is measured relative crystallinity (Fig. 1) (is benchmark with C) with xrd method (carrying out) on Rigaku D/max-II type x-ray powder diffraction instrument, SEM photo (Fig. 2, Fig. 3) absorbs on Philips XL30D6716 instrument, acceleration voltage is 20KV, measure silica alumina ratio with IR spectrography (carrying out on Perkin-Elmer 983G type raster pattern infrared spectrometer), data are listed in the table 1.By data in the table as can be seen, with the pretreated coal gangue of acidleach deferrization is that the degree of crystallinity of the product of feedstock production has reached more than 85%, surpassing traditional is the degree of crystallinity 10-20% of feedstock production X zeolite method products obtained therefrom with the coal gangue, and product whiteness also is much improved; The adding of crystal seed has certain promoter action to degree of crystallinity and the shortening crystallization time that improves product.The SEM photo shows the X type zeolite of the coal gangue preparation after the deferrization, and grain growing is complete, and homogeneous grain diameter (about 2.5um) does not have other stray crystal.Experiment showed, that the method that improves the degree of crystallinity of zeolite by deironing is fully feasible, provide may thereby the industry for preparing high-quality X type zeolite for coal gangue large-scale develops and utilizes.
Claims (4)
1. one kind is the method for feedstock production high-crystallinity X-type zeolite with the coal gangue, it is characterized in that the feed coal spoil is dipped in the acid deferrization liquid, stirs deferrization, and suction filtration is washed to neutrality then, and high temperature alkali fuse is aging again, hydrothermal crystallizing, and actual conditions is:
(1) raw material of preparation high-crystallinity X-type zeolite is that coal gangue and other are main with the silico-aluminate
The mineral substance of composition;
(2) used deferrization agent is an acidic solution, the consumption of acid solution H in the acid solution
+Mole number and coal gangue
The ratio of quality represents that its scope is (0.0005～0.1) molH
+/ g coal gangue;
(3) before the activation of coal gangue high temperature alkali fuse, the acidleach deferrization, leaching time is 15-480 minute, acidleach
Temperature is 0-100 ℃;
Adding or do not add crystal seed when (4) wearing out, is product of roasting quality≤10% if add its add-on.
2. prepare the method for high-crystallinity X-type zeolite by claim 1 is described with coal gangue, it is characterized in that used deferrization acidic solution is HCl, H
2SO
4, HNO
3, H
2C
2O
4, the acid solution consumption is 0.005～0.04molH
+/ g coal gangue.
3. prepare the method for high-crystallinity X-type zeolite by claim 1 is described with coal gangue, the acidleach temperature when it is characterized in that deferrization is 20-80 ℃, leaching time 20-120 minute.
4. according to claim 1ly prepare the method for high-crystallinity X zeolite with coal gangue, the amount that it is characterized in that adding in the weathering process crystal seed is product of roasting quality≤5%, but does not comprise 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00119586A CN1093087C (en) | 2000-08-10 | 2000-08-10 | Process for preparing high-crystallinity X-type zeolite from coal gangue as raw material |
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|---|---|---|---|
| CN00119586A CN1093087C (en) | 2000-08-10 | 2000-08-10 | Process for preparing high-crystallinity X-type zeolite from coal gangue as raw material |
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|---|---|
| CN1280956A CN1280956A (en) | 2001-01-24 |
| CN1093087C true CN1093087C (en) | 2002-10-23 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254928B (en) * | 2007-02-28 | 2010-06-23 | 中国石油化工股份有限公司 | Method for preparing fine-grain low silica/alumina ratio X zeolite |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106219568A (en) * | 2016-06-22 | 2016-12-14 | 内蒙古大学 | A kind of method utilizing gangue to prepare high-purity molecular sieve ZSM 5 |
| CN106865565A (en) * | 2017-03-26 | 2017-06-20 | 天津大学 | A kind of flyash synthesizes the method for X-type zeolite |
| CN107352554B (en) * | 2017-07-31 | 2020-04-21 | 西安科技大学 | Preparation method and application of magnetic X-type molecular sieve |
| CN111337447B (en) * | 2020-03-20 | 2021-09-24 | 中国矿业大学 | Coal and gangue bionic identification system and method |
| CN112209399A (en) * | 2020-09-11 | 2021-01-12 | 内蒙古师范大学 | Method for preparing X-type zeolite from coal gangue |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5253787A (en) * | 1975-10-29 | 1977-04-30 | Toray Ind Inc | Adsorbent compoition |
| 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 |
| CN1148568A (en) * | 1992-10-05 | 1997-04-30 | 气体产品与化学公司 | Crystalline X-zeolite |
-
2000
- 2000-08-10 CN CN00119586A patent/CN1093087C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5253787A (en) * | 1975-10-29 | 1977-04-30 | Toray Ind Inc | Adsorbent compoition |
| 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 |
| CN1148568A (en) * | 1992-10-05 | 1997-04-30 | 气体产品与化学公司 | Crystalline X-zeolite |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254928B (en) * | 2007-02-28 | 2010-06-23 | 中国石油化工股份有限公司 | Method for preparing fine-grain low silica/alumina ratio X zeolite |
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| Publication number | Publication date |
|---|---|
| CN1280956A (en) | 2001-01-24 |
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