阅读说明：本技术 一种循环流化床粉煤灰制备p型沸石和f型八面沸石的方法 (A kind of method of circulating fluid bed coal ash preparation P type zeolite and F type faujasite ) 是由 张丽宏 郭彦霞 薛芳斌 程芳琴 于 2019-08-12 设计创作，主要内容包括：一种循环流化床粉煤灰制备P型沸石和F型八面沸石的方法,属于工业固体废弃物的资源化利用及沸石合成技术领域,目的在于提供一种有效解决粉煤灰固废消纳的技术,粉煤灰经过酸处理,除去铁和钙等杂元素,然后再经过焙烧碱熔处理,在一种晶体导向剂作用下,通过改变导向剂加入前后的搅拌工艺,可控制备不同品质的P型沸石和F型八面沸石两种沸石。本方法实现了利用一种粉煤灰在同一种晶体导向剂作用下得到两种沸石。(A kind of method of circulating fluid bed coal ash preparation P type zeolite and F type faujasite, belong to the resource utilization and zeolite synthesis technical field of industrial solid castoff, it is designed to provide a kind of technology for effectively solving the consumption of flyash solid waste, flyash is through peracid treatment, except the miscellaneous element such as de-iron and calcium, then using roasting alkali fusion processing, under a kind of effect of crystal directed agents, the stirring technique that front and back is added by changing directed agents, two kinds of zeolites of P type zeolite and F type faujasite of controllable preparation difference quality.This method, which is realized, obtains two kinds of zeolites under the effect of same crystal directed agents using a kind of flyash.)

1. a kind of method of circulating fluid bed coal ash preparation P type zeolite and F type faujasite, it is characterised in that: including as follows Step:

The first step, acid processing: circulating fluid bed coal ash and 10-25% hydrochloric acid are mixed for the ratio of 1:3-1:5g/mL with solid-to-liquid ratio It closes, 1-2h, filtering and washing is stirred at 800-100 DEG C；

Second step, alkali fusion processing: according to mass ratio being the ratio of 0.5-2 by sodium hydroxide and first step acid treated flyash Example is uniformly mixed, and after grinding, at 450-650 DEG C, is roasted 1-2h, is ground after cooling；

Third step, hydrothermal synthesis P type zeolite: being added distilled water into second step treated flyash, makes solid and liquid Mass volume ratio is 1:3-1:12g/mL, and stirring ageing 0-60min, is then added the nothing for accounting for distilled water volume 3-10% at room temperature Machine directed agents, stir evenly, and at 100 DEG C, hydrothermal crystallizing 12-20h, after the reaction was completed, filtering and washing to pH are 8-10, dry After obtain P type zeolite；

4th step, hydrothermal synthesis F type zeolite: being added distilled water into second step treated flyash, makes solid and liquid Mass volume ratio is 1:3-1:12g/mL, and stirring ageing 0-60min, is then added the nothing for accounting for distilled water volume 3-10% at room temperature Machine directed agents continue to stir 20min-12h, and then at 100 DEG C, hydrothermal crystallizing 12-20h, after the reaction was completed, filtering and washing is extremely PH is 8-10, obtains F type zeolite after dry.

2. the method for a kind of circulating fluid bed coal ash preparation P type zeolite and F type faujasite according to claim 1, It is characterized by: the inorganic directing agent the preparation method is as follows:

NaAlO is added in deionized water₂, after completely dissolution, NaOH is added, it is 3.3, quality point that modulus is added while stirring Number is the liquid sodium silicate of 34wt%, so that NaOH:Al₂O₃: SiO₂: H₂The mol ratio of O is 10-20:1:10-20:230- 430, continue after stirring 10min, 1 h of stirring in water bath at 65 DEG C takes out, is cooled to room temperature, obtains inorganic directing agent.

3. the method for a kind of circulating fluid bed coal ash preparation P type zeolite and F type faujasite according to claim 1, It is characterized by: the solid-to-liquid ratio of circulating fluid bed coal ash described in the first step and hydrochloric acid is 1g:3mL.

4. the method for a kind of circulating fluid bed coal ash preparation P type zeolite and F type faujasite according to claim 1, It is characterized by: the mass ratio of sodium hydroxide described in second step and acid treated flyash is 1.1-1.5.

5. the method for a kind of circulating fluid bed coal ash preparation P type zeolite and F type faujasite according to claim 1, It is characterized by: the mass volume ratio of solid described in third step and liquid is 1:3-1:6g/mL, the additional amount of inorganic directing agent Accounting for distilled water volume is 5-10%.

6. the method for a kind of circulating fluid bed coal ash preparation P type zeolite and F type faujasite according to claim 1, It is characterized by: the mass volume ratio of solid described in the 4th step and liquid is 1:3-1:6g/mL, the additional amount of inorganic directing agent Accounting for distilled water volume is 5-10%.

Technical field

The invention belongs to the resource utilization of industrial solid castoff and zeolite synthesis technical fields, and in particular to Yi Zhonghuan Fluid-bed fly ash for P type zeolite and F type faujasite method.

Background technique

Flyash is one of the main solid waste that coal-burning power plant generates, and yield is up to 600,000,000 tons or more.Currently, powder Coal ash is widely used in building materials, builds work field, and utilization rate reaches 70%, a large amount of heaps of flyash that residue is not utilized effectively Deposit and not only occupy valuable land resource, and due to fugitive dust, be discharged into the modes such as water system serious influence produced on environment. Main component is silica and aluminium oxide in flyash, much like in composition with zeolite.Not according to the type of furnace and coal class Together, flyash is divided into coal-powder boiler flyash and circulating fluid bed coal ash.Silicon existence form in coal-powder boiler flyash mainly has Invisible type, mullite and three kinds of quartz, aluminium are primarily present in the mullite phase for being difficult to activate, and silicon in circulating fluid bed coal ash It is main exist in the form of quartzy, aluminium mainly exists with amorphous forms.In comparison, in circulating fluid bed coal ash silicon and Aluminium is easier to be activated in low-temperature alkaline condition.

Zeolite product can be used as adsorbent, ion-exchanger, catalyst etc., and have good practical application value. It therefore is a kind of with good economic value and utilization approaches by being prepared into zeolite molecular sieve by flyash.

P type zeolite have two-dimensional channel structure, in aqueous solution calcium ions and magnesium ions and micro-molecular gas have good choosing Selecting property.Currently, coal-powder boiler flyash synthesis P type zeolite has document report.Using sodium carbonate under 800 DEG C of high temperature calcining and activating powder Coal ash, hydrothermal synthesis P type zeolite (silicate notification, 2016,35(3): 922-926；Silicate notification, 2009,28(3): 468- 472；Chemical Journal of Chinese Universities, 2015,36(2): 229-235).This method maturing temperature is high, and energy consumption is higher.Coal-powder boiler fine coal Ash passes through alkali soluble, is separated by solid-liquid separation, and prepares p-type (coal science and technology, 2007,35(11) using supernatant liquor: 84-86).Coal dust Furnace flyash directly prepares P type zeolite (Dalian Polytechnic University's journal, 2009,28(1) after alkali soluble: 44-47).These methods Lower to the utilization rate of flyash, product contains a large amount of inertia miscellaneous phase, and product purity is lower.Patent (201210506177.X) report Coal-powder boiler flyash is first passed through hydrochloric acid (liquid-solid ratio of hydrochloric acid and flyash is 9mL/g -11mL/g) processing by road, using The sodium hydroxide and potassium hydroxide of 4mol/L mixes aqueous slkali in 70-80 DEG C of processing 2h.Acid amount is larger in this method, and uses hydrogen The two kinds of high concentration mixed alkali liquor processing of potassium oxide and sodium hydroxide, the especially higher cost of potassium hydroxide, and will cause one Quantitative amorphous phase silicon loss, subsequent increase silica flour dosage.

F type faujasite has three-dimensional open-framework, can be applied to metal ion removal and petrochemical industry.Document report Road is first prepared into geo-polymer using flyash as raw material, then synthesize F type faujasite (artificial lens journal, 2018,47 (2): 411-417).It is raw material after acidic leaching with alkaline is molten that such as application No. is 201610662749.1 using coal-powder boiler flyash, is carried out Hydrothermal crystallizing obtains F type faujasite.

Summary of the invention

The purpose of the present invention is to provide a kind of technologies for effectively solving the consumption of flyash solid waste, are total utilization of PCA Sial scheme new using offer simultaneously in the process；The low in raw material price of use, synthesis cost are low；Synthesis process is industrially Simple and easy, energy consumption is lower；By simply regulating and controlling stirring ageing process, the P type zeolite and F type of two kinds of different qualities can be synthesized Faujasite.

The present invention adopts the following technical scheme:

A kind of method of circulating fluid bed coal ash preparation P type zeolite and F type faujasite, includes the following steps:

The first step, acid processing: circulating fluid bed coal ash and 10-25% hydrochloric acid are mixed for the ratio of 1:3-1:5g/mL with solid-to-liquid ratio It closes, stirs 1-2h at 800-100 DEG C, except the miscellaneous elements such as de-iron and calcium, filtering and washing；

Second step, alkali fusion processing: according to mass ratio being the ratio of 0.5-2 by sodium hydroxide and first step acid treated flyash Example is uniformly mixed, and after grinding, at 450-650 DEG C, is roasted 1-2h, is ground after cooling；

Third step, hydrothermal synthesis P type zeolite: being added distilled water into second step treated flyash, makes solid and liquid Mass volume ratio is 1:3-1:12g/mL, and stirring ageing 0-60min, is then added the nothing for accounting for distilled water volume 3-10% at room temperature Machine directed agents, stir evenly, and at 100 DEG C, hydrothermal crystallizing 12-20h, after the reaction was completed, filtering and washing to pH are 8-10, dry After obtain P type zeolite；

4th step, hydrothermal synthesis F type zeolite: being added distilled water into second step treated flyash, makes solid and liquid Mass volume ratio is 1:3-1:12g/mL, and stirring ageing 0-60min, is then added the nothing for accounting for distilled water volume 3-10% at room temperature Machine directed agents continue to stir 20min-12h, and then at 100 DEG C, hydrothermal crystallizing 12-20h, after the reaction was completed, filtering and washing is extremely PH is 8-10, obtains F type zeolite after dry.

The inorganic directing agent the preparation method is as follows:

NaAlO is added in deionized water₂, after completely dissolution, NaOH is added, it is 3.3, quality point that modulus is added while stirring Number is the liquid sodium silicate of 34wt%, so that NaOH:Al₂O₃: SiO₂: H₂The mol ratio of O is 10-20:1:10-20:230- 430, continue after stirring 10min, 1 h of stirring in water bath at 65 DEG C takes out, is cooled to room temperature, obtains inorganic directing agent.

Further, the solid-to-liquid ratio of circulating fluid bed coal ash described in the first step and hydrochloric acid is 1g:3mL.

Further, the mass ratio of sodium hydroxide described in second step and acid treated flyash is 1.1-1.5.

Further, the mass volume ratio of solid described in third step and liquid is 1:3-1:6g/mL, inorganic directing agent It is 5-10% that additional amount, which accounts for distilled water volume,.

Further, the mass volume ratio of solid described in the 4th step and liquid is 1:3-1:6g/mL, inorganic directing agent It is 5-10% that additional amount, which accounts for distilled water volume,.

Beneficial effects of the present invention are as follows:

1. the present invention using industrial waste circulating fluid bed coal ash as raw material, had not only realized the resource utilization of flyash, but also closed At can widely applied P type zeolite and F type faujasite.

2. the present invention using circulating fluid bed coal ash as raw material, under a kind of effect of crystal directed agents, is oriented to by changing The stirring technique of front and back, two kinds of zeolites of P type zeolite and F type faujasite of controllable preparation difference quality are added in agent.By simple Operation realizes a kind of coal ash for manufacturing for two kinds of high-valued products, and the economic value of product significantly improves.

Detailed description of the invention

Fig. 1 is the XRD diagram of circulating fluid bed coal ash of the present invention.

Fig. 2 is the XRD diagram of the P type zeolite of the embodiment of the present invention 1.

Fig. 3 is the XRD diagram of the P type zeolite of the embodiment of the present invention 2.

Fig. 4 is the XRD diagram of the F type zeolite of the embodiment of the present invention 3.

Fig. 5 is the XRD diagram of the F type zeolite of the embodiment of the present invention 4.

Specific embodiment