CN1254681A - Processf or preparing X-zeolite from coal gangue - Google Patents
Processf or preparing X-zeolite from coal gangue Download PDFInfo
- Publication number
- CN1254681A CN1254681A CN 99119981 CN99119981A CN1254681A CN 1254681 A CN1254681 A CN 1254681A CN 99119981 CN99119981 CN 99119981 CN 99119981 A CN99119981 A CN 99119981A CN 1254681 A CN1254681 A CN 1254681A
- Authority
- CN
- China
- Prior art keywords
- coal gangue
- type zeolite
- hour
- produce
- alkali fusion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A process for preparing X-zeolite from coal gangue-containing various inertial silicon or aluminium oxides includes such steps as high-temp alkali fusion, activating and hydrothermal synthesis. Its advantages are low cost, simple operation, high repeatability, and high purity and crystallinity of obtained X-zeolite.
Description
The present invention is a kind of method of producing X type zeolite with coal gangue.
Coal gangue is the by product that obtains in the coal mining process, and its main component is a silicon, aluminium, calcium, magnesium, the oxide compound of iron etc. and a spot of carbon.The produced quantity of coal gangue is very big, can reach the 10-20% of raw coal output.If do not add processing, let alone to be deposited in around the colliery, not only occupy a large amount of farmlands, and also often spontaneous combustion, discharging obnoxious flavour, rain drop erosion also can wash some toxic substances under the inflow place serious environment pollution.Therefore fully utilizing coal gangue has very high economic benefit and social benefit.
At present, the utilization of coal gangue mainly contains the following aspects: 1) act as a fuel, utilize wherein a small amount of combustiblecomponents.2) make material of construction, as perforated brick, spoil cement etc.3) make industrial raw material, extract A1C1
3, TiO
2, SiO
2Deng industrial chemicals.But all there is the shortcoming that economic value added is not high or the material effective component utilization ratio is low in above-mentioned approach.Thinking of the present invention is to make full use of main body composition sieve and silica-sesquioxide in the coal gangue, and preparation reaches other field widely used X type zeolite in fractionation by adsorption in ion-exchange and the catalysis.
In recent years, Feng Fangxia etc. reported once that extracting went out some of aluminium with strong acid contact process active coal gangue, the synthetic ZSM-35 of hydro-thermal under alkaline condition then, the method for high silica alumina ratio zeolites such as mordenite (1. Feng Fangxia, Dou Tao, Shi Yanjun etc.Petroleum journal (refining of petroleum), 1997,13 (4): 104; 2. Feng Fangxia, Dou Tao, Shi Yanjun etc.Petroleum journal (refining of petroleum), 1999,15 (1): 75).But this method is higher to the coal gangue quality requirements, and the coal gangue raw material must be purer kaolin, and the coal gangue of actual extraction always contains the sieve and silica-sesquioxide of other type, and as quartz etc., thereby aforesaid method does not possess universality.Secondly if will the aluminium that be gone out by the strong acid extracting in this method be used, need more complicated technological process.And this method synthetic zeolite actual demand amount is also little.
The objective of the invention is to invent a kind of easy method, realize producing purity with coal gangue, the X type zeolite that degree of crystallinity is all higher.
Coal gangue raw material used in the present invention can be various types of coal gangues, be the different places of production, the coal gangue that composition differs, be meant the coal gangue and flyash and the various types of clay class natural mineral matter that do not contain and contain alpha-quartz and other sieve and silica-sesquioxide dephasign, said alkali fusion agent is meant all kinds of sodium type alkali, NaOH for example, Na
2CO
3, NaHCO
3, Na
2SO
3, Na
2C
2O
4, NaOAc etc.
The method for preparing X type zeolite that the present invention relates to is as follows:
1. raw material and alkali fusion agent are evenly dried the back by the predetermined proportion thorough mixing;
2. mixture is warming up to preset temperature under air atmosphere, reaction for some time;
3. after the question response product is cooled to room temperature, add suitable quantity of water, under agitation condition, aging for some time;
4. will be transferred in the stainless steel cauldron through the aged mixture, at a certain temperature crystallization for some time;
5. the product after the crystallization is filtered, washing gets product after the drying.
The alkali fusion agent is the Na in the sodium type alkali among the present invention
2SiO in O and the coal gangue
2Mol ratio, Na
2O/SiO
2=(1.0-3.0), Na wherein
2O is from NaOH, Na
2CO
3, NaHCO
3, Na
2SO
3, Na
2C
2O
4, NaOAc etc., SiO
2From raw material.
It is 500-1000 ℃ that raw material mixes the post-reacted temperature of oven dry, and the reaction times is 0.5-10 hour, after reaction product is cooled to room temperature, adds water and stirs agingly, and amount of water is to make the molarity of NaOH, C
NaOHBe 1.0-5.0mol/L, wherein suppose the alkali fusion agent after treatment, sodium wherein all exists with the NaOH form, and digestion time is 0.5-40 hour; Aging back is 25-150 ℃ of following crystallization, and crystallization time is 0.5 hour-40 hours.
According to above-mentioned condition, the present invention can obtain better effect in following ranges:
Na in the alkali fusion agent
2SiO in O and the coal gangue
2Mol ratio, Na
2O/SiO
2=1.5-2.0; It is 800-900 ℃ that raw material mixes the post-reacted temperature of oven dry, reacts 2-4 hour; Add water aged amount of water after the reaction and be and make C
NaOH=2.0-3.0mol/L, digestion time is 10-15 hour; Crystallization temperature is 80-120 ℃, and crystallization time is 8-12 hour; Product after the crystallization is filtered, and washing gets product after the drying.
The invention provides the method that is equipped with X type zeolite by coal gangue high temperature alkali fuse legal system.This method is easy and simple to handle, and is cheap, coal gangue main body composition sieve and silica-sesquioxide utilization ratio height, and prepared X type zeolite purity, degree of crystallinity is all higher, and application prospect is extensive.
Below example will be further described the method for producing X type zeolite by coal gangue provided by the invention.Data in the example are listed in the specification sheets subordinate list with diagrammatic form, wherein have:
Fig. 1 alkali fusion product, conventional synthesis method product, the part character of commodity X type zeolite is relatively;
Fig. 2 alkali fusion agent add-on is to the influence of alkali fusion product degree of crystallinity;
Fig. 3 alkali fusion agent add-on is too high, crosses low influence to alkali fusion product degree of crystallinity;
Fig. 4 water add-on is to alkali fusion, the influence of conventional synthesis method product degree of crystallinity;
Fig. 5 crystallization time is for the influence of alkali fusion product degree of crystallinity.
Example 1
Getting 1g is crushed to colliery, tafelberg, 100 purpose Henan seven ore deposit spoils (it basic composition is 4.56%C, 50.4%SiO
2, 25.2%Al
2O
3, rest part is mainly magnesium, calcium, the oxide compound of iron etc.The XRD figure spectrum shows that main crystalline phase is kaolinite and alpha-quartz.) and the 1.69g anhydrous Na
2CO
3(make Na
2O/SiO
2Mol ratio=1.9) in porcelain mortar, mix.Mixture is transferred in the porcelain boat.Porcelain boat is placed in the tube furnace roasting under air atmosphere.Earlier 120 ℃ of constant temperature 1 hour, to eliminate planar water, then the speed with 15-20 ℃/min was warming up to 850 ℃, constant temperature 3 hours.After treating that the alkali fusion thing is cooled to room temperature, it is transferred in the plastic test tube, adds 11.4g distilled water and (make C
NaOH=2.8mol/L), and under the magnetic agitation condition, aged at room temperature 12 hours.To react feed liquid and be transferred in the stainless steel cauldron, 100 ℃ of crystallization 10 hours.Crystallization product is through suction strainer, and washing promptly gets X type zeolite product after the drying.This product is designated as A.
Example 2
Get the above-mentioned coal gangue of 1g, add the NaOH strong solution and (contain 1.28gNaOH, make Na
2O/SiO
2Mol ratio=1.9), mix the back oven dry.Below operation is identical with example 1.Product is designated as B.
Comparative Examples 1
With water glass, NaAlO
2, NaOH is the synthetic X type zeolite of raw material.Reaction conditions is SiO
2/ Al
2O
3Mol ratio=3.4, Na
2O/SiO
2Mol ratio=1.9, C
NaOH=2.8mol/L, under agitation condition, aged at room temperature 12 hours, 100 ℃ of hydrothermal crystallizings 10 hours.Product is designated as C.
Comparative Examples 2
Commodity X type zeolite by Sinoamerican Joint Venture Jinzhong Molecular Sieves Co., Ltd., Shanghai's production.This product is designated as D.
Example 3
The XRD figure spectrum of the said products shows that all X is unique crystalline phase.The said products is measured relative crystallinity (is benchmark with D) with xrd method,, measure water adsorption amount and benzene adsorptive capacity, on ASAP-2000 type physical adsorption appearance, measure N with the atmospheric flow method with IR spectrographic determination silica alumina ratio
2The adsorption-desorption thermoisopleth calculates specific surface according to the Langmuir method again, calculates micropore pore volume (micropore finger-hole footpath is less than the hole of 2nm) according to the t-plot method.Data are listed among Fig. 1.The silica alumina ratio of four kinds of products is very approaching, so the XRD ratio of peak can be represented relative crystallinity.Two kinds of alkali fusion products obtained therefrom A are though the relative crystallinity of B has also reached higher numerical value not as good as the products C of conventional synthesis method gained.In addition, adsorptive capacity, specific surface, the relative ratio of micropore pore volume and relative crystallinity numerical value basically identical just list out the relative crystallinity (all with D as benchmark) of product in therefore following each example.
Example 3-6
Press example 1 described method and handle coal gangue, but regulate Na
2CO
3Add-on, make Na
2O/SiO
2Mol ratio equals 1.5,1.7,1.9,2.1 respectively.Product is designated as A1, A2, A3, A4 respectively.
Example 7-10
Press example 2 described methods and handle coal gangue, but regulate the add-on of NaOH, make Na
2O/SiO
2Mol ratio equals 1.5,1.7,1.9,2.1 respectively.Product is designated as B1, B2, B3, B4 respectively.
A1-4, the relative crystallinity data of B1-4 are listed among Fig. 2.Two kinds of alkali fusion reaction systems are not very sensitive for the alkali add-on as shown in Figure 2, at Na
2O/SiO
2All can obtain the higher X type zeolite of degree of crystallinity in the mol ratio 1.5-2.1 scope.
Comparative Examples 3-6
Press example 1 described method and handle coal gangue, but regulate Na
2CO
3Add-on, make Na
2O/SiO
2Mol ratio equals 1.1,1.3,2.3,2.5 respectively.Product is designated as E1, E2, E3, E4 respectively.Wherein E1 is an amorphous substance, obviously is mixed with A type zeolite in other three products, and the relative crystallinity data of the X type zeolite that they are contained are listed among Fig. 3.As shown in Figure 3, when the alkali add-on is too high or too low, can't make degree of crystallinity ideal X type zeolite by alkali fusion.
Example 11-14
Press example 2 described methods and handle coal gangue, but regulate and the alkali fusion thing blended water yield, make C
NaOHEqual 2.2,2.4,2.6 respectively, 2.8mol/L.Product is designated as B5, B6, B7, B8 respectively.
Comparative Examples 7-10
Handle coal gangue by Comparative Examples 1 described method, but regulate institute's amount of water, make C
NaOHEqual 2.2,2.4,2.6 respectively, 2.8mol/L.Product is designated as C1, C2, C3, C4 respectively.
B5-8, the relative crystallinity data of C1-4 are listed among Fig. 4.Alkali fusion reaction system and conventional synthesis method reaction system are all very sensitive for the water yield as shown in Figure 4, but both response modes are opposite.For the alkali fusion reaction system, the water yield is low more, and the degree of crystallinity of gained X type zeolite is high more.This result helps reducing the running cost of alkali fusion.
Comparative Examples 11-14
Press the described method of example 7-10 and handle coal gangue, but change the alkali fusion temperature into 750 ℃.Product is designated as F1, F2, F3, F4 respectively.F1-4 all is an amorphous substance.This result shows that the alkali fusion temperature is the key factor in the building-up process.
Example 15-19
Press example 1 described method and handle coal gangue, but change crystallization time into 3,6,10,14 respectively, 18 hours.Products obtained therefrom is designated as A5, A6, A7, A8, A9 respectively.A8 wherein, A9 obviously contains sodalite.The relative crystallinity data of contained X type zeolite are listed among Fig. 5 among the A5-9.The required crystallization time of alkali fusion reaction system is longer as shown in Figure 5, but long crystallization time can cause changeing crystalline substance.
Claims (7)
1. produce the method for X type zeolite with coal gangue for one kind, the coal gangue raw material is mixed reaction at a certain temperature after the oven dry with the alkali fusion agent, aging then, crystallization is characterized in that:
(1) alkali fusion agent, the Na in the promptly all kinds of sodium type alkali
2SiO in O and the coal gangue
2Mol ratio Na
2O/SiO
2=(1.0-3.0);
(2) the post-reacted temperature of raw material mixing oven dry is 500-1000 ℃;
(3) the above-mentioned reaction times is 0.5-10 hour;
(4) adding water stirring aged amount of water after reaction finishes is C
NaOH=1.0-5.0mol/L
(5) digestion time is 0.5-40 hour;
(6) crystallization temperature is 25-150 ℃;
(7) crystallization time is 0.5-40 hour.
2. according to claim 1ly produce the method for X type zeolite with coal gangue, the amount that it is characterized in that the alkali fusion agent is Na
2O/SiO
2Be 1.5-2.0.
3. according to claim 1ly produce the method for X type zeolite, it is characterized in that it is 800-900 ℃ that raw material mixes the post-reacted temperature of oven dry with coal gangue.
4. according to claim 1ly produce the method for X type zeolite, it is characterized in that the reaction times is 2-4 hour with coal gangue.
5. according to claim 1ly produce the method for X type zeolite, it is characterized in that amount of water makes C with coal gangue
NaOH=2.0-3.0mol/L.
6. according to claim 1ly produce the method for X type zeolite, it is characterized in that digestion time is 10-15 hour with coal gangue.
7. according to claim 1ly produce the method for X type zeolite with coal gangue, it is characterized in that crystallization temperature is 80-120 ℃, crystallization time is 8-12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119981A CN1093088C (en) | 1999-11-09 | 1999-11-09 | Processf or preparing X-zeolite from coal gangue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119981A CN1093088C (en) | 1999-11-09 | 1999-11-09 | Processf or preparing X-zeolite from coal gangue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1254681A true CN1254681A (en) | 2000-05-31 |
| CN1093088C CN1093088C (en) | 2002-10-23 |
Family
ID=5281270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99119981A Expired - Fee Related CN1093088C (en) | 1999-11-09 | 1999-11-09 | Processf or preparing X-zeolite from coal gangue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1093088C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116106C (en) * | 2000-08-10 | 2003-07-30 | 复旦大学 | Preparation of activated carbon-zeolite composition with coal gangue |
| CN102774856A (en) * | 2012-07-25 | 2012-11-14 | 中国环境科学研究院 | Method for preparing w-shaped zeolite molecular sieve by taking Hanggin soil 2# as raw material |
| CN102774853A (en) * | 2012-07-25 | 2012-11-14 | 中国环境科学研究院 | Method for preparing X-shaped zeolite molecular sieve by taking Hanggin soil 2# as raw material |
| CN107352554A (en) * | 2017-07-31 | 2017-11-17 | 西安科技大学 | A kind of preparation method and application of magnetic X-type molecular sieve |
| CN111943223A (en) * | 2020-08-27 | 2020-11-17 | 武汉大学 | Method for preparing X-type zeolite by utilizing coal gangue and rice hulls |
| CN112209399A (en) * | 2020-09-11 | 2021-01-12 | 内蒙古师范大学 | Method for preparing X-type zeolite from coal gangue |
| CN112691696A (en) * | 2020-12-23 | 2021-04-23 | 华电电力科学研究院有限公司 | Preparation method of aromatization catalyst taking coal gangue as raw material |
| CN114988426A (en) * | 2022-06-06 | 2022-09-02 | 西安科技大学 | Coal gangue-based molecular sieve and alkali fusion-hydrothermal preparation method thereof |
-
1999
- 1999-11-09 CN CN99119981A patent/CN1093088C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116106C (en) * | 2000-08-10 | 2003-07-30 | 复旦大学 | Preparation of activated carbon-zeolite composition with coal gangue |
| CN102774856A (en) * | 2012-07-25 | 2012-11-14 | 中国环境科学研究院 | Method for preparing w-shaped zeolite molecular sieve by taking Hanggin soil 2# as raw material |
| CN102774853A (en) * | 2012-07-25 | 2012-11-14 | 中国环境科学研究院 | Method for preparing X-shaped zeolite molecular sieve by taking Hanggin soil 2# as raw material |
| CN102774853B (en) * | 2012-07-25 | 2014-06-25 | 中国环境科学研究院 | Method for preparing X-shaped zeolite molecular sieve by taking Hanggin soil 2# as raw material |
| CN102774856B (en) * | 2012-07-25 | 2014-06-25 | 中国环境科学研究院 | Method for preparing w-shaped zeolite molecular sieve by taking Hanggin soil 2# as raw material |
| CN107352554A (en) * | 2017-07-31 | 2017-11-17 | 西安科技大学 | A kind of preparation method and application of magnetic X-type molecular sieve |
| CN107352554B (en) * | 2017-07-31 | 2020-04-21 | 西安科技大学 | Preparation method and application of magnetic X-type molecular sieve |
| CN111943223A (en) * | 2020-08-27 | 2020-11-17 | 武汉大学 | Method for preparing X-type zeolite by utilizing coal gangue and rice hulls |
| CN112209399A (en) * | 2020-09-11 | 2021-01-12 | 内蒙古师范大学 | Method for preparing X-type zeolite from coal gangue |
| CN112691696A (en) * | 2020-12-23 | 2021-04-23 | 华电电力科学研究院有限公司 | Preparation method of aromatization catalyst taking coal gangue as raw material |
| CN114988426A (en) * | 2022-06-06 | 2022-09-02 | 西安科技大学 | Coal gangue-based molecular sieve and alkali fusion-hydrothermal preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1093088C (en) | 2002-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Inada et al. | Synthesis of zeolite from coal fly ashes with different silica–alumina composition | |
| CN1093088C (en) | Processf or preparing X-zeolite from coal gangue | |
| RU2516536C2 (en) | Photocatalytic composite materials, containing titanium and limestone free from titanium dioxide | |
| CN1281495C (en) | Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material | |
| CN1116106C (en) | Preparation of activated carbon-zeolite composition with coal gangue | |
| WO1994026662A1 (en) | Aluminosilicates | |
| CN115385356B (en) | Method for preparing 13X molecular sieve by utilizing fly ash solid phase | |
| CN106946267A (en) | A kind of EU-1 molecular sieves and its synthetic method | |
| CN113234234B (en) | Method for preparing aluminum-based metal-organic framework material by using high-alumina fly ash | |
| EP1027285B1 (en) | Process for production of zeolites from raw materials containing alkali alumino hydro-silicates | |
| CN1084711C (en) | Method for synthesizing zeolite molecular sieve using minerals as raw material | |
| JPH11292538A (en) | Production of zirconia-ceria composition | |
| CN110894074B (en) | A zeolite molecular sieve and preparation method thereof | |
| CN108579662B (en) | Preparation of SiO from low-grade kaolin2/Al2O3Method for compounding materials | |
| CN1280956A (en) | Process for preparing high-crystallinity X-type zeolite from coal gangue as raw material | |
| JPH07196315A (en) | Method for synthesizing zeolite | |
| Chaudhuri et al. | Synthesis and Characterization of Detergent‐Grade Zeolite from Indian Clay | |
| CN86104439A (en) | A kind of compound coagulant and method for making thereof and purposes | |
| CN1083399C (en) | Synthesis of high-silicon mordenite | |
| CN100358807C (en) | Selective preparation method for zeolite | |
| CN1769171A (en) | Zeolite molecular sieve preparation method | |
| CN1631780A (en) | Method for producing 4A molecular sieve by using waste liquid of NaY molecular sieve production | |
| CN1013436B (en) | The preparation of cordierite precursor | |
| CN1093513C (en) | Process for synthesizing zeolite with mordenite structure | |
| CN104340990A (en) | Method for synthesizing zeolite Y |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |