阅读说明：本技术 一种动态自调节水热法制备a型粉煤灰基分子筛的方法 (Method for preparing A-type fly ash-based molecular sieve by dynamic self-regulation hydrothermal method ) 是由 王琪 王晓龙 宋润 刘练波 郜时旺 邱会哲 于 2020-05-13 设计创作，主要内容包括：本发明公开了一种动态自调节水热法制备A型粉煤灰基分子筛的方法。该方法可以使用中铝或低铝粉煤灰为原料,加入NaOH碱溶,同时粉煤灰晶化滤液循环利用,经球磨、筛分、干燥预处理后以一定比例配料,通过自动取样在线分析和自主优化方法,动态自适应调节碱溶过程的硅铝溶出速率,经陈化后,动态自适应调节晶化过程,确保晶型和生产率。本发明能够充分利用粉煤灰自身硅铝元素,不添加额外硅源、铝源,过程能耗低、经济性好、废水和固废排放少,生产效率高,工艺操作简便,产品质量稳定一致性好。(The invention discloses a method for preparing an A-type fly ash-based molecular sieve by a dynamic self-regulation hydrothermal method. According to the method, medium-aluminum or low-aluminum fly ash can be used as a raw material, NaOH is added for alkali dissolution, fly ash crystallization filtrate is recycled, the fly ash crystallization filtrate is subjected to ball milling, screening and drying pretreatment and then is mixed in a certain proportion, the silicon-aluminum dissolution rate in the alkali dissolution process is dynamically and adaptively adjusted through an automatic sampling online analysis and autonomous optimization method, and the crystallization process is dynamically and adaptively adjusted after aging, so that the crystal form and the production rate are ensured. The method can fully utilize the silicon-aluminum elements of the fly ash, does not add additional silicon sources and aluminum sources, and has the advantages of low process energy consumption, good economy, less discharge of waste water and solid waste, high production efficiency, simple and convenient process operation, and stable and consistent product quality.)

1. A method for preparing an A-type fly ash-based molecular sieve by a dynamic self-regulating hydrothermal method is characterized by comprising the following steps:

1) pretreatment: ball-milling the fly ash, screening to obtain fine powder with the particle size of less than 75 microns, and performing drying pretreatment;

2) preparing materials: adding the fly ash obtained by pretreatment in the step 1) and 0.5-10 mol/L NaOH solution into a reactor according to the liquid-solid ratio of 0.5-10 mL/g, and adding fly ash crystallized filtrate with the volume ratio of the fly ash to the NaOH solution of 1: 5-1: 1 into the reactor;

3) dynamically and adaptively adjusting alkali dissolution and aging: setting the initial alkali dissolution temperature of a reactor, dynamically stirring the reactor at a set rotating speed, automatically sampling materials in a balance pipe connected with the reactor according to a preset sampling period, automatically filtering, performing element analysis on a liquid phase, automatically adjusting the alkali dissolution temperature and the stirring rotating speed in real time by using a PLC (programmable logic controller) or DCS (distributed control system) system according to the silicon-aluminum ratio of the liquid phase, finishing alkali dissolution and beginning aging when the ratio of the sum of the silicon-aluminum ion concentration and the sodium ion concentration reaches a critical value and the silicon-aluminum ratio meets a set range, wherein the aging temperature is 0-60 ℃, the aging time is 1-72 hours, and the aging rotating speed is 25-500 r/min;

4) dynamic self-adaptive adjustment and crystallization: setting the initial crystallization temperature of a reactor, dynamically stirring the reactor at a set rotating speed, automatically sampling materials in a balance pipe connected with the reactor according to a preset sampling period, automatically filtering the materials, then carrying out element analysis on a liquid phase, carrying out in-situ Raman spectrum analysis on a solid phase, automatically adjusting the crystallization temperature, the crystallization time and the stirring rotating speed in real time by using a PLC (programmable logic controller) or DCS (distributed control system) system according to the Si and Al element analysis result of the liquid phase and the in-situ Raman spectrum analysis result of the solid phase, and stopping crystallization and cooling after the Si and Al element analysis result of the liquid phase and the in-situ Raman analysis result of the solid phase reach the product requirement or reach the maximum crystallization time;

5) and (3) post-treatment: filtering the crystallized product obtained in the step 4) to obtain filter residue and filtrate, and washing, drying and roasting the filter residue to obtain the A-type fly ash-based molecular sieve.

2. The method of claim 1, wherein in step 3), the initial alkali dissolution temperature is 80 ℃, the alkali dissolution temperature is controlled within a range of 50-120 ℃, the initial stirring speed is 500r/min, the stirring speed is controlled within a range of 25-1000 r/min, the critical value of the ratio of the sum of the concentrations of the silicon and aluminum ions to the concentration of the sodium ion is 0.2-1.3, and the silicon-aluminum ratio is set within a range of 1.5-2.5.

3. The method of claim 1, wherein in the step 4), the initial crystallization temperature is 90 ℃, the crystallization temperature is controlled within a range of 60-150 ℃, the initial stirring speed is 75r/min, the stirring speed is controlled within a range of 20-200 r/min, and the crystallization time is controlled within a range of 0.1-120 h.

4. The method of claim 1, wherein the autonomous optimization method in steps 3) and 4) is a constrained simplex algorithm, a neural network algorithm, or an artificial intelligence algorithm.

5. The method for preparing the A-type fly ash-based molecular sieve according to claim 1, wherein the A-type fly ash-based molecular sieve obtained in the step 5) has a Si/Al ratio of 1.8-2.5 and a specific surface area of 50-287 m²/g。

Technical Field

The invention relates to the technical field of coal ash utilization and zeolite molecular sieve production, in particular to a method for preparing an A-type coal ash-based molecular sieve by a dynamic self-regulating hydrothermal method.

Background

Fly ash is a solid particulate matter recovered from flue gas after coal combustion, and China generates hundreds of millions of tons of fly ash every year. At present, in western regions of China, a large amount of fly ash is not utilized, and is simply accumulated, so that pollution is brought to water, soil and atmosphere, and human health is harmed. The fly ash is mainly used for building materials and road construction, has low additional value, and has important significance for developing a new way of utilizing the fly ash, particularly for developing high-additional-value products.

The content of silicon and aluminum in the fly ash can account for 50-80% of the total content, and the composition is similar to that of a molecular sieve. The A-type molecular sieve has low silica-alumina ratio and polar hydrophilicity, and can be used for gas dehydration and drying. The common 4A molecular sieve is Na-type aluminosilicate with a porous structure, the pore diameter is 0.4nm, and the 3A molecular sieve with the pore diameter of 0.3nm or the 5A molecular sieve with the pore diameter of 0.5nm can be obtained by performing K or Ca ion exchange on the aluminosilicate. In recent years, many researchers have studied on the preparation of zeolite a molecular sieves from fly ash and developed related technologies.

CN101928009B discloses a method for preparing a 4A type molecular sieve for a detergent, which adopts desiliconized liquid generated in a pre-desiliconization process section in an aluminum oxide preparation process by using high-alumina fly ash as a silicon source, and sodium aluminate crude liquid obtained in a clinker dissolution process section as an aluminum source to prepare the 4A type molecular sieve through two steps of gelatinizing and crystallizing. CN103553069B discloses a preparation method of submicron 4A zeolite, which takes high-alumina fly ash produced by a power plant as a raw material, prepares sodium silicate as a silicon source by alkali-soluble pre-desiliconization, takes clinker-dissolved sodium aluminate as an aluminum source, and prepares the submicron 4A zeolite by two main procedures of low-temperature homogenization at 30-70 ℃ and high-temperature crystallization at 70-90 ℃. CN101693542B discloses a method for producing a 4A molecular sieve, which comprises the steps of taking an intermediate product sodium silicate solution or white carbon black obtained by extracting silicon dioxide by a fly ash alkali dissolution method as a silicon source, taking sodium aluminate or aluminum hydroxide obtained by preparing aluminum oxide by a fly ash desilication ash sintering method as an aluminum source, stirring to form gel, adding a guiding agent, and standing at 70-100 ℃ for crystallization to obtain the 4A molecular sieve.

CN104773740 discloses a method for synchronously preparing A-type zeolite and white carbon black by utilizing fly ash, wherein the fly ash after iron powder is removed by magnetic separation is subjected to Na treatment₂CO₃Melting, washing with water, performing hydrothermal crystallization at 80-100 ℃, filtering, washing and drying to obtain the 4A molecular sieve. CN106745042A discloses a method for preparing 4A type molecular sieve and ZSM-5 type molecular sieve by using Chinese fly ash acid method aluminum extraction residue, which comprises the steps of carrying out alkali fusion roasting on the fly ash acid method aluminum extraction residue, washing and filtering, and carrying out CO filtration₂And (4) carrying out carbon separation and crystallization at 90-110 ℃ to obtain the 4A molecular sieve. CN101367529 discloses a method for synthesizing a 4A molecular sieve by a fly ash alkali fusion method, which is to melt fly ash with the alumina content of 36-46% and the silica-alumina ratio of 1.8-2.1 at 550-800 ℃ with alkali, add water for dissolving, gelatinize at 50-80 ℃, standing at 100 +/-10 ℃ for crystallization, wash and dry to obtain the 4A molecular sieve.

However, the prior art still has the defects that: most of the technologies rely on byproducts in the production process of producing alumina by using high-alumina fly ash, and the fly ash with common aluminum content and low aluminum content is difficult to treat and has poor economical efficiency; in part of the technologies, silicon sources and aluminum sources are required to be additionally added, so that the synthesis cost of the molecular sieve is greatly increased; the obtaining of an aluminum source needs acid dissolution, and excessive acid needs alkali neutralization, so that the process economy is reduced, or the high-temperature melting by an alkali method increases the energy consumption and the equipment investment is high; the standing crystallization method has harsh required conditions, long production period and low production efficiency; the crystallized alkaline waste liquid cannot be economically recycled, or the quality of the molecular sieve product prepared by recycling is not easy to be well controlled; the partial technology processes one ton of fly ash to generate more than two tons of waste, which not only does not play a role in utilizing solid waste resources, but also increases the waste.

Disclosure of Invention

The invention provides a method for preparing an A-type fly ash-based molecular sieve by a dynamic self-adjusting hydrothermal method, which overcomes the defects of the prior art, is suitable for producing a 4A zeolite molecular sieve by various fly ashes, particularly medium-aluminum and low-aluminum fly ashes, completely takes the fly ashes as a silicon source and an aluminum source without adding additional silicon source and aluminum source, not only aims at the utilization rate of the fly ashes but also focuses on the economy, high efficiency, low energy consumption, low emission and environmental protection of the whole process, effectively controls the product quality, and does not influence the consistency of the product due to the difference of the chemical composition and mineral activity of the fly ashes.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for preparing an A-type fly ash-based molecular sieve by a dynamic self-regulating hydrothermal method comprises the following steps:

1) pretreatment: ball-milling the fly ash, screening to obtain fine powder with the particle size of less than 75 microns, and performing drying pretreatment;

2) preparing materials: adding the fly ash obtained by pretreatment in the step 1) and 0.5-10 mol/L NaOH solution into a reactor according to the liquid-solid ratio of 0.5-10 mL/g, and adding fly ash crystallized filtrate with the volume ratio of the fly ash to the NaOH solution of 1: 5-1: 1 into the reactor;

3) dynamically and adaptively adjusting alkali dissolution and aging: setting the initial alkali dissolution temperature of a reactor, dynamically stirring the reactor at a set rotating speed, automatically sampling materials in a balance pipe connected with the reactor according to a preset sampling period, automatically filtering, performing element analysis on a liquid phase, automatically adjusting the alkali dissolution temperature and the stirring rotating speed in real time by using a PLC (programmable logic controller) or DCS (distributed control system) system according to the silicon-aluminum ratio of the liquid phase, finishing alkali dissolution and beginning aging when the ratio of the sum of the silicon-aluminum ion concentration and the sodium ion concentration reaches a critical value and the silicon-aluminum ratio meets a set range, wherein the aging temperature is 0-60 ℃, the aging time is 1-72 hours, and the aging rotating speed is 25-500 r/min;

4) dynamic self-adaptive adjustment and crystallization: setting the initial crystallization temperature of a reactor, dynamically stirring the reactor at a set rotating speed, automatically sampling materials in a balance pipe connected with the reactor according to a preset sampling period, automatically filtering the materials, then carrying out element analysis on a liquid phase, carrying out in-situ Raman spectrum analysis on a solid phase, automatically adjusting the crystallization temperature, the crystallization time and the stirring rotating speed in real time by using a PLC (programmable logic controller) or DCS (distributed control system) system according to the Si and Al element analysis result of the liquid phase and the in-situ Raman spectrum analysis result of the solid phase, and stopping crystallization and cooling after the Si and Al element analysis result of the liquid phase and the in-situ Raman analysis result of the solid phase reach the product requirement or reach the maximum crystallization time;

5) and (3) post-treatment: filtering the crystallized product obtained in the step 4) to obtain filter residue and filtrate, and washing, drying and roasting the filter residue to obtain the A-type fly ash-based molecular sieve.

Further, in the step 3), the initial alkali dissolution temperature is 80 ℃, the alkali dissolution temperature control range is 50-120 ℃, the initial stirring rotation speed is 500r/min, the stirring rotation speed is 25-1000 r/min, the critical value of the ratio of the sum of the silicon-aluminum ion concentration and the sodium ion concentration is 0.2-1.3, and the set range of the silicon-aluminum ratio is 1.5-2.5.

Further, in the step 4), the initial crystallization temperature is 90 ℃, the crystallization temperature control range is 60-150 ℃, the initial stirring rotation speed is 75r/min, the stirring rotation speed control range is 20-200 r/min, and the crystallization time control range is 0.1-120 h.

Further, the autonomous optimization method in steps 3) and 4) is a constrained simplex algorithm, a neural network algorithm or an artificial intelligence algorithm.

Further, the A-type fly ash-based molecular sieve obtained in the step 5) has a silicon-aluminum ratio of 1.8-2.5 and a specific surface area of 50-287 m²/g。

Compared with the prior art, the invention has the following beneficial technical effects:

the fly ash prepared by the method has wide applicability and can be suitable for medium-aluminum and low-aluminum fly ash. The method has the advantages of no use of high-temperature alkali fusion, dynamic regulation and control of the silicon-aluminum ratio of the molecular sieve, full utilization of silicon-aluminum elements of the fly ash, no addition of additional silicon source and aluminum source, low process energy consumption, good economical efficiency and less discharge of waste water and solid waste. The dynamic method has the advantages of high production efficiency, simple and convenient process operation, small influence of the nonuniformity of the fly ash on products, stable quality, good consistency and no other zeolite impurities. Small particle size, convenient later-stage forming, rich pore channels, and specific surface area up to 287m²Per g, good adsorption performance.

Drawings

FIG. 1 is the XRD patterns obtained in examples 1, 2 and 3, wherein A is the characteristic diffraction peak of zeolite A molecular sieve, and Q is the characteristic peak of inert highly crystalline quartz phase originally contained in fly ash.

Detailed Description

The invention is described in further detail below for a better understanding of the invention.

A method for preparing an A-type fly ash-based molecular sieve by a dynamic self-regulating hydrothermal method comprises the following steps:

1) pretreatment: ball-milling the fly ash, screening to obtain fine powder with the particle size of less than 75 microns, and drying for 24 hours at 100 ℃;

2) preparing materials: adding the fly ash obtained by pretreatment in the step 1) and 0.5-10 mol/L NaOH solution into a reactor according to the liquid-solid ratio of 0.5-10 mL/g, and adding fly ash crystallized filtrate with the volume ratio of the fly ash to the NaOH solution of 1: 5-1: 1 into the reactor.

3) Dynamically and adaptively adjusting alkali dissolution and aging: setting the initial alkali dissolution temperature of a reactor to be 80 ℃, dynamically stirring the reactor at a rotating speed of 500r/min, automatically sampling materials in a balance pipe connected with the reactor according to a preset period, automatically filtering, performing element analysis on a liquid phase, and automatically adjusting the alkali dissolution temperature and the stirring rotating speed in real time by a PLC (programmable logic controller) or DCS (distributed control system) system by adopting an autonomous optimization method (a constraint simplex algorithm, a neural network algorithm or an artificial intelligence algorithm) according to the silicon-aluminum ratio of the liquid phase, wherein the alkali dissolution temperature is controlled within a range of 50-120 ℃, the stirring rotating speed is controlled within a range of 25-1000 r/min, when the ratio of the sum of the silicon-aluminum ion concentrations and the sodium ion concentration reaches a critical value of 0.2-1.3 and the silicon-aluminum ratio accords with a set range of 1.5-2.5, finishing the alkali dissolution, starting aging, the aging temperature is 0-60 ℃, the aging time is 1-72 hours.

4) Dynamic self-adaptive adjustment and crystallization: setting the initial crystallization temperature of the reactor to be 90 ℃, dynamically stirring the reactor at the initial rotating speed of 75r/min, automatically sampling materials in a balance pipe connected with the reactor according to a preset period, automatically filtering the materials, performing elemental analysis on a liquid phase, and (2) carrying out in-situ Raman spectrum analysis on the solid phase, adopting an autonomous optimization method (a constrained simplex algorithm, a neural network algorithm or an artificial intelligence algorithm) according to the analysis result of Si and Al elements of the liquid phase and the analysis result of the in-situ Raman spectrum of the solid phase, and automatically adjusting the crystallization temperature, the crystallization time and the stirring rotating speed in real time by a PLC (programmable logic controller) or DCS (distributed control system) system, wherein the crystallization temperature control range is 60-150 ℃, the stirring rotating speed control range is 20-200 r/min, the crystallization time control range is 0.1-120 h, and crystallization is stopped and cooled after the analysis result of Si and Al elements of the liquid phase and the analysis result of the in-situ Raman spectrum of the solid phase.

5) And (3) post-treatment: and filtering the obtained crystallized product to obtain filter residue and filtrate, and washing, drying and roasting the filter residue to obtain the A-type fly ash-based molecular sieve.

The present invention is described in further detail below with reference to examples: