阅读说明：本技术 Fcc废催化剂作为吸附剂处理废水污染物的方法 (Method for treating wastewater pollutants by using FCC (fluid catalytic cracking) waste catalyst as adsorbent ) 是由 刘政伟 张宏哲 房师平 张志远 郭磊 牟桂琴 于 2019-03-15 设计创作，主要内容包括：本发明涉及一种FCC废催化剂作为吸附剂处理废水污染物的方法,主要解决现有技术中FCC废催化剂利用价值低、废水处理成本高的问题。本发明通过采用一种FCC废催化剂作为吸附剂处理废水污染物的方法,以未改性的FCC废催化剂或酸改性后的FCC废催化剂作为吸附剂,控制废水溶液pH为2-12、温度为20-95℃、固液比为0.1-100mg/L,吸附废水中重金属离子和/或有机污染物；所述重金属离子为Hg<Sup>2+</Sup>、Cu<Sup>2+</Sup>、Ni<Sup>2+</Sup>、Cd<Sup>2+</Sup>、Pb<Sup>2+</Sup>、Zn<Sup>2+</Sup>、Cr<Sup>3+</Sup>、Fe<Sup>2+</Sup>、Fe<Sup>3+</Sup>、Mn<Sup>2+</Sup>中的至少一种,所述有机污染物为酚类、芳烃、腈类、醛类、苯胺、硝基苯、甲基橙、氨氮中的至少一种的技术方案较好地解决了上述问题,可用于处理废水污染物中。(The invention relates to a method for treating wastewater pollutants by using an FCC (fluid catalytic cracking) waste catalyst as an adsorbent, which mainly solves the problems of low utilization value of the FCC waste catalyst and high wastewater treatment cost in the prior art. The invention adopts a method for treating wastewater pollutants by using an FCC waste catalyst as an adsorbent, and uses an unmodified FCC waste catalyst or an acid-modified FCC waste catalyst as the adsorbentThe adsorbent is used for adsorbing heavy metal ions and/or organic pollutants in the wastewater by controlling the pH of the wastewater solution to be 2-12, the temperature to be 20-95 ℃ and the solid-to-liquid ratio to be 0.1-100 mg/L; the heavy metal ions are Hg 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Pb 2+ 、Zn 2+ 、Cr 3+ 、Fe 2+ 、Fe 3+ 、Mn 2+ The organic pollutant is at least one of phenols, aromatic hydrocarbons, nitriles, aldehydes, aniline, nitrobenzene, methyl orange and ammonia nitrogen, and the technical scheme can better solve the problems and can be used for treating wastewater pollutants.)

1. A method for treating wastewater pollutants by using an FCC spent catalyst as an adsorbent comprises the steps of using an unmodified FCC spent catalyst or an acid-modified FCC spent catalyst as an adsorbent, controlling the pH of a wastewater solution to be 2-12, the temperature to be 20-95 ℃, and the solid-liquid ratio to be 0.1-100mg/L, and adsorbing heavy metal ions and/or organic pollutants in wastewater; the heavy metal ions are Hg²⁺、Cu²⁺、Ni²⁺、Cd²⁺、Pb²⁺、Zn²⁺、Cr³⁺、Fe²⁺、Fe³⁺、Mn²⁺The organic pollutant is at least one of phenols and aromaticsAt least one of hydrocarbon, nitrile, aldehyde, aniline, nitrobenzene, methyl orange and ammonia nitrogen.

2. The method for treating wastewater pollutants by using FCC spent catalyst as adsorbent in accordance with claim 1, wherein the unmodified FCC spent catalyst is a spent balancer directly discharged from a catalytic cracking unit, and has a particle size of 30-150 μm, an average particle size of 70-90 μm, and a specific surface area of 250-300m²/g。

3. The method as claimed in claim 1, wherein the acid-modified spent FCC catalyst is obtained by activating a spent balancer discharged from a catalytic cracking unit in an acid solution having a certain concentration at a certain temperature, and removing contaminant ions including Ni, Fe, V, Sb, which are easily leached from the channels and surfaces of the spent FCC catalyst, by activation, thereby preventing cross-contamination and increasing the specific surface area of the spent FCC catalyst, wherein the specific surface area after activation is 305-550 m-²/g。

4. The method for treating wastewater pollutants by using FCC spent catalyst as adsorbent according to claim 3, characterized in that the acid is HCl, HNO₃、H₂SO₄Or acetic acid, the acid concentration is 0.5-5 wt%, and the activation temperature is 20-90 deg.C.

5. The method for treating wastewater pollutants by using FCC spent catalyst as an adsorbent according to claim 4, wherein the acid is HCl, the acid concentration is 1-3 wt%, and the activation temperature is 40-80 ℃.

6. The method for treating wastewater pollutants by using FCC spent catalyst as adsorbent in accordance with claim 1, wherein the FCC spent catalyst to be acid-modified has a specific surface area of 100-249m²/g。

7. The method for treating wastewater pollutants by using FCC spent catalyst as adsorbent according to claim 1, wherein the solid-to-liquid ratio is 2-20mg/L, depending on the kind and concentration of the pollutants to be adsorbed in the wastewater.

8. The method for treating wastewater pollutants using FCC spent catalyst as a sorbent as claimed in claim 1, wherein the temperature of the wastewater solution is controlled to be 30-60 ℃.

9. The method for treating wastewater pollutants by using FCC spent catalyst as an adsorbent according to claim 1, wherein the heavy metal ions and organic pollutants in the wastewater are adsorbed by using unmodified FCC spent catalyst or acid-modified FCC spent catalyst as the adsorbent.

10. The method for treating wastewater pollutants using FCC spent catalyst as claimed in claim 8, wherein the temperature of the wastewater solution is controlled to 40-50 ℃.

Technical Field

The invention relates to a method for treating heavy metal ions and organic pollutants in wastewater by using an FCC (fluid catalytic cracking) waste catalyst as an adsorbent.

Background

Fluid Catalytic Cracking (FCC) is one of heavy oil lightening processes commonly used in the petroleum refining industry, and the adopted FCC catalysts are classified into amorphous silica-alumina catalysts and molecular sieve catalysts, both of which use silica and alumina as main components, and in the using process, the catalyst activity is reduced and the reaction selectivity is deteriorated due to the impact of high temperature, poison, coking, mechanical abrasion, thermal disintegration and the like, so that the catalyst becomes a waste catalyst.

At present, the domestic FCC waste catalyst is generally treated by adopting a landfill method, and the landfill treatment of the waste catalyst not only occupies a large amount of land resources, but also does not realize the reuse of the waste catalyst, so that how to reasonably treat the FCC waste catalyst is an important subject concerned by the industry.

The fresh FCC catalyst is a porous substance, is mostly microporous, has an average pore diameter of 4-7nm, has an extremely large specific surface area of up to 600-²Is a good adsorbent. Although the chemical reaction activity and selectivity of the FCC spent catalyst are reduced due to the impact of high temperature, poison, coking, mechanical abrasion, thermal disintegration and the like, the specific surface area of the catalyst is only slightly reduced,still up to 100-300m²The product has strong adsorption capacity, and can be used as adsorbent.

US3960760A teaches that FCC spent catalyst can be used as water adsorbent to remove ammonium ions in sewage and heavy metal ions in industrial wastewater to purify municipal or industrial wastewater after being activated with NaOH aqueous solution at a certain temperature, not only reducing dust pollution and land waste caused by waste catalyst dust landfill, but also making full use of waste. The patent mainly utilizes the untreated or NaOH alkaline activated FCC spent catalyst to adsorb heavy metal ions, and the alkaline activation can destroy the aluminum-silicate framework of the FCC spent catalyst. The literature, "foreign catalytic cracking spent catalyst treatment and utilization" (journal: environmental protection of petrochemical industry, 1989) describes that Mobil corporation, USA, utilizes FCC spent catalyst without any treatment as an adsorbent to adsorb soluble and solid harmful chemicals in wastewater. This document uses an untreated FCC waste catalyst, in some cases, a phenomenon that heavy metal ions on the surface of the catalyst are dissolved into waste water occurs, and the specific surface area of the waste catalyst which is not activated is much smaller than that of acid activation, and this document is mainly used for organic pollutants.

The price of the active carbon adsorbent in the current market is about 1 ten thousand yuan/t, the price of the granular clay adsorbent is about 4500 yuan/t, the service cycle is generally 2-3 months, and the use price is high. And a 100-million ton/year catalytic cracking unit discharges thousands of tons of waste catalyst every year. Therefore, compared with the conventional activated carbon or clay which is commonly used at present, the waste FCC catalyst or the modified waste FCC catalyst is used as the adsorbent for treating the waste water, and the large specific surface area is utilized to realize the treatment of waste by waste, thereby reducing the cost for treating the waste water, finding a way for the waste catalyst and generating better economic benefit and social benefit.

Disclosure of Invention

The invention aims to solve the technical problems of low utilization value of the FCC waste catalyst and high wastewater treatment cost in the prior art, provides a novel method for treating wastewater pollutants by using the FCC waste catalyst as an adsorbent, and has the advantages of high utilization value of the FCC waste catalyst and low wastewater treatment cost.

In order to solve the problems, the technical scheme adopted by the invention is as follows: a method for treating wastewater pollutants by using an FCC spent catalyst as an adsorbent comprises the steps of using an unmodified FCC spent catalyst or an acid-modified FCC spent catalyst as an adsorbent, controlling the pH of a wastewater solution to be 2-12, the temperature to be 20-95 ℃, and the solid-liquid ratio to be 0.1-100mg/L, and adsorbing heavy metal ions and/or organic pollutants in wastewater; the heavy metal ions are Hg²⁺、Cu²⁺、Ni²⁺、Cd²⁺、Pb²⁺、Zn²⁺、Cr³⁺、Fe²⁺、Fe³⁺、Mn²⁺The organic pollutant is at least one of phenols, aromatic hydrocarbons, nitriles, aldehydes, aniline, nitrobenzene, methyl orange and ammonia nitrogen.

In the above technical solution, preferably, the unmodified FCC spent catalyst is a spent equilibrium agent directly discharged from a catalytic cracking unit, and has a particle size of 30-150 μm, an average particle size of 70-90 μm, and a specific surface area of 250-300m²/g。

In the above technical scheme, preferably, the acid-modified FCC waste catalyst is obtained by activating a waste balancer discharged from a catalytic cracking unit in an acid solution with a certain concentration at a certain temperature, and removing pollution ions including Ni, Fe, V, and Sb, which are easily leached from the pore channels and the surface of the FCC waste catalyst, by activation, so as to prevent cross contamination, and simultaneously improve the specific surface area of the waste catalyst, wherein the specific surface area after activation is 305-²/g。

In the above technical solution, preferably, the acid is HCl or HNO₃、H₂SO₄Or acetic acid, the acid concentration (mass concentration) is 0.5-5%, and the activation temperature is 20-90 deg.C.

In the above technical solution, preferably, the acid is HCl, the acid concentration (mass concentration) is 1-3%, and the activation temperature is 40-80 ℃.

In the above technical scheme, preferably, the specific surface area of the FCC spent catalyst needing acid modification is 100-249m²/g。

In the above technical solution, preferably, the solid-to-liquid ratio is 2-20mg/L, which is determined according to the kind and concentration of the pollutant to be adsorbed in the wastewater.

In the above technical scheme, preferably, the temperature of the wastewater solution is controlled to be 30-60 ℃, more preferably, 40-50 ℃.

In the above technical solution, preferably, the unmodified FCC waste catalyst or the acid-modified FCC waste catalyst is used as an adsorbent to adsorb heavy metal ions and organic pollutants in the wastewater.

The invention relates to a method for adsorbing heavy metal ions and organic pollutants in waste water by utilizing catalytic cracking (FCC) waste catalyst, which takes unmodified FCC waste catalyst or modified FCC waste catalyst as an adsorbent, adjusts parameters such as pH, temperature, solid-liquid ratio and the like of the waste water, and adsorbs Hg in the waste water²⁺,Cu²⁺,Ni²⁺,Cd²⁺,Pb²⁺,Zn²⁺,Cr³⁺,Fe²⁺,Fe³⁺,Mn²⁺And heavy metal ions and organic pollutants such as phenols, aromatic hydrocarbons, nitriles, aldehydes, aniline, nitrobenzene, methyl orange, ammonia nitrogen and the like. The method mainly utilizes the untreated or acid-treated FCC spent catalyst to adsorb metal ions and organic matters, and acid activation is to dissolve impurities deposited on the particle surface of the FCC spent catalyst so as to improve the specific surface area. The process is simple, the pore size of the FCC spent catalyst is uniformly distributed, the specific surface area is large, the adsorption effect on pollutants in the wastewater is good, the wastewater treatment cost is reduced, the resource recycling of the FCC spent catalyst is realized, and better economic benefit and social benefit are generated.

The present invention will be further illustrated by the following examples, but is not limited to these examples.

Detailed Description