WO2017128600A1

WO2017128600A1 - Ozone catalytic oxidation catalyst for wastewater treatment and preparation method therefor

Info

Publication number: WO2017128600A1
Application number: PCT/CN2016/086231
Authority: WO
Inventors: 李国文; 张玉芬; 王彦成; 张学辉; 高阳; 毛文君; 余伟齐
Original assignee: 北京纬纶华业环保科技股份有限公司; 凯姆德（北京）能源环境科技有限公司
Priority date: 2016-01-30
Filing date: 2016-06-17
Publication date: 2017-08-03
Also published as: CN105536813A

Abstract

A catalyst for the process of ozone catalytic oxidation of wastewater, consisting of an active component, an auxiliary and a carrier. The active component is a transition metal oxide, the auxiliary is an alkali metal oxide, an alkaline earth metal oxide or a lanthanide metal oxide, and the carrier is aluminium oxide, active carbon or ceramsite. The active component, auxiliary and dispersing agent are supported on a carrier by using an impregnation method or a dry mixing method, and the catalyst is then prepared by drying and calcinating.

Description

Ozone catalytic oxidation catalyst for wastewater treatment and preparation method thereof

The present application claims priority to Chinese Patent Application No. 201610067238.5, entitled "Ozone Catalytic Oxidation Catalyst for Wastewater Treatment and Preparation Method thereof", which is filed on January 30, 2016, the entire contents of which are incorporated by reference. The citations are incorporated herein by reference.

Technical field

The invention belongs to the technical field of water treatment, in particular to an ozone catalytic oxidation catalyst for wastewater treatment and a preparation method thereof.

Background technique

With the development of society, more and more synthetic compounds enter the water body, causing some high-stability, difficult-to-oxidize organic substances in the water body, which cause serious damage to the water environment. The cost-effective removal of such refractory organic pollutants from water has become a hot spot in research and engineering applications in the field of water treatment.

In recent years, advanced oxidation technology using ozone as an oxidant has been able to oxidize and decompose toxic and refractory organic pollutants in water, and has received increasing attention. Although simple ozone can degrade organic matter, it is selective and has a small reaction rate with aromatic organic compounds. In many cases, organic matter cannot be completely oxidized. Therefore, the ozone process has been improved by adding a catalyst. Catalytic ozone oxidation technology is divided into two types according to the different catalysts used: one is a homogeneous catalytic ozonation technology using metal ions as a catalyst; the other is a heterogeneous catalytic ozonation technique using a solid catalyst. The existing catalytic ozone oxidation technology has the characteristics of mild reaction conditions, high oxidation activity and no secondary pollution, but at the same time has the problems of low COD removal rate of the catalyst, complicated catalyst preparation process and short catalyst life, which needs further improvement.

Summary of the invention

It is an object of the present invention to provide an ozone catalytic oxidation catalyst for wastewater treatment and a preparation method thereof to solve the above problems.

The invention provides an ozone catalytic oxidation catalyst for wastewater treatment, the catalyst is composed of an active component, an auxiliary agent and a carrier; wherein the active component is a transition metal oxide, and the auxiliary agent is an alkali metal oxide or an alkaline earth metal. An oxide or a lanthanide metal oxide; the support is alumina, activated carbon or ceramsite.

Further, the active component is from 1.0% to 15% by mass, and the auxiliary is from 0.1% to 1.0%, with the balance being a carrier.

Further, the active component is one or more transition metal oxides selected from the group consisting of titanium, manganese, iron, cobalt, nickel, copper, and zinc.

Further, the auxiliary agent is one or more alkali metal oxides, alkaline earth metal oxides or lanthanide metal oxides selected from the group consisting of sodium, potassium, magnesium, calcium, strontium, barium.

The invention also provides a preparation method of an ozone catalytic oxidation catalyst for wastewater treatment, that is, a precursor compound of an active component and a precursor compound of an auxiliary agent are supported on a carrier by a dipping method or a dry mixing method, and the health is maintained. Prepared after drying and calcining; the precursor compound of the active component is a salt compound of a transition metal; the precursor compound of the auxiliary is an alkali metal salt compound, an alkaline earth metal salt compound or a lanthanide series a metal salt compound; the carrier is alumina, activated carbon or ceramsite.

Further, the active component in the catalyst is 1.0% to 15% by mass, and the auxiliary agent is 0.1% to 1.0% by mass, and the balance is a carrier.

Further, the method specifically includes:

The precursor compound of the active component and the precursor compound of the auxiliary agent are formulated into a mixed impregnation liquid A;

Adding a dispersing agent to the mixed impregnation liquid A to prepare a mixed impregnation liquid B;

The mixed impregnation liquid B is supported on a carrier, and then the catalyst is obtained by curing, drying, and calcining.

Further, when the mixed impregnation liquid A is prepared, the precursor compound of the active component and the precursor compound of the auxiliary agent are respectively mixed in the form of a precursor compound solution of the active component and a precursor compound solution of the auxiliary agent. The impregnation liquid A, the precursor compound of the active component in the precursor compound solution of the active component has a metal ion mass concentration of 1% to 15%; the precursor compound of the auxiliary agent in the precursor compound solution of the auxiliary agent The metal ion has a mass concentration of 1% to 15%.

Further, the dispersant is added in an amount of from 100 to 1000 g/L.

Further, the baking temperature is 400 to 800 ° C, and the baking time is 2 to 6 hours.

Compared with the prior art, the invention has the beneficial effects of higher COD removal rate and service life. The life is longer, the preparation process is simple, the cost is low, and there is no secondary pollution, which is very suitable for industrial production.

detailed description

In order to further understand the present invention, the preferred embodiments of the present invention are described in the accompanying drawings.

An embodiment of the present invention provides an ozone catalytic oxidation catalyst comprising: an active component, an auxiliary agent and a carrier; and the active component is from 1.0% to 15% by mass, preferably from 5.0% to 15% by mass, More preferably, it is 8.0%-15%; the auxiliary agent in the invention is 0.1%-1.0%, preferably 0.3%-1.0%; the balance is a carrier; wherein the active component is a transition metal oxide, and the auxiliary agent is an alkali metal An oxide, an alkaline earth metal oxide or a lanthanide metal oxide; the support is alumina, activated carbon or ceramsite.

In an embodiment of the invention, the active component is one or more transition metal oxides selected from the group consisting of titanium, manganese, iron, cobalt, nickel, copper, and zinc.

In an embodiment of the invention, the adjuvant is one or more alkali metal oxides, alkaline earth metal oxides or lanthanide metal oxides selected from the group consisting of sodium, potassium, magnesium, calcium, strontium, barium.

The invention also provides a preparation method of an ozone catalytic oxidation catalyst for wastewater treatment, which adopts a dipping method or a dry mixing method to load a precursor compound of an active component and a precursor compound of an auxiliary agent on a carrier, The catalyst is prepared after curing, drying and roasting. In order to uniformly load the precursor compound of the active component and the precursor compound of the auxiliary agent on the carrier, it is preferred to further add a dispersing agent in the present invention, that is, the precursor compound of the active component is assisted by dipping or dry mixing. The precursor compound of the agent and the dispersing agent are supported on a carrier, and the catalyst is prepared by curing, drying and calcining; in the present invention, the preparation method is preferably a dipping method; in the later calcination process, the dispersing agent is decomposed.

Wherein, the precursor compound of the active component is a precursor compound containing an active component ion well known to those skilled in the art, and is not particularly limited. In the present invention, a salt compound of a transition metal is preferred, and more preferably It is a soluble salt compound of a transition metal; the precursor compound of the auxiliary agent is a precursor compound containing a metal ion of a promoter well known to those skilled in the art, and is not particularly limited, and an alkali metal salt is preferred in the present invention. One or more of a compound, an alkaline earth metal salt compound, and a lanthanide metal salt compound; in an embodiment of the present invention Wherein, the active component in the catalyst is from 1.0% to 15% by mass, preferably from 0.1% to 1.0%, and the balance is a carrier; wherein the preferred range of the active component and the adjuvant content As described above, it will not be repeated here; the active component is a transition metal oxide, the auxiliary agent is an alkali metal oxide, an alkaline earth metal oxide or a lanthanide metal oxide; the dispersing agent is phosphorus, silicon, boron, nitrogen, sulfur. Or a halogen compound; the carrier is alumina, activated carbon or ceramsite.

In an embodiment of the invention, the method specifically includes:

The mixed impregnation liquid B is supported on a carrier by dipping or dry mixing, and then the catalyst is prepared by standing, standing, curing, and calcining at room temperature. The method for preparing the catalyst in the examples of the present invention is preferably a dipping method, and still more preferably an equal volume dipping method.

In the embodiment of the present invention, the mixed impregnation liquid A has a mass concentration of 1%-15%, that is, the mass concentration of the metal ions in the transition metal, alkali metal or alkaline earth metal or lanthanide metal ion solution is 1%-15%. .

In the embodiment of the present invention, the dispersant is added in an amount of 100 to 1000 g/L, preferably in an amount of 100 to 800 g/L.

In an embodiment of the invention, the calcination temperature is 400-800 ° C and the calcination time is 2-6 h.

Embodiments of the present invention provide a preferred distribution of active components by the addition of a dispersant during the preparation of the catalyst. The dispersing agent in the embodiment of the present invention is a surfactant having excellent dispersing property and wettability, and has a function of uniformly dispersing a plurality of metal salts on the surface of the pores of the carrier, which is provided by the embodiment of the present invention. The ozone catalytic oxidation catalyst has higher COD removal rate, longer service life and simple preparation process. After ozone-catalyzed oxidation treatment, the COD removal rate in refinery reverse osmosis concentrated water can reach more than 60%, and the biodegradability BOD/COD of wastewater is increased to more than 0.30; the COD removal rate in phenol-containing wastewater can reach about 90%. . And no secondary pollution, low cost, very suitable for industrial production.

In addition, the catalyst provided by the embodiment of the invention is not limited to the catalytic oxidation treatment of refining and reverse osmosis concentrated water, and is also suitable for treating reverse osmosis concentrated water of other systems such as coal chemical reverse osmosis concentrated water and oil recovery reverse osmosis concentrated water. At the same time, it is also suitable for wastewater treatment of other systems, such as treatment of phenol-containing wastewater, including Waste water of ester compounds, aromatic hydrocarbon compounds, and small molecule acids.

In order to further illustrate the technical solutions of the present invention, the preferred embodiments of the present invention are described in the accompanying drawings.

The chemical reagents used in the examples of the present invention are all commercially available.

Example 1 Preparation of Fe-Mn-Na/Alumina Catalyst

(1) Fe(NO ₃ ) ₃ , Mn(NO ₃ ) ₂ , and a NONO ₃ solution of 170 ml, 43 ml, and 17 ml each having a metal ion concentration of 1 wt.% were mixed to prepare a mixed impregnation liquid A.

(2) To the above mixed impregnation liquid A, 100 g of octadecyltrimethylammonium bromide was added to prepare a mixed impregnation liquid B.

(3) The mixed impregnating solution B was spray-impregnated on 500 g of the shaped alumina carrier by an equal volume impregnation method, and then sealed for 4 h, dried at 100 ° C for 5 h, and finally calcined at 400 ° C for 4 h to obtain a catalyst A.

Example 2 Preparation of Fe-Cu-K/Activated Carbon Catalyst

(1) Fe(NO ₃ ) ₃ , Cu(NO ₃ ) ₂ , and KNO ₃ solutions of 170 ml, 80 ml, and 10 ml each having a metal ion concentration of 15 wt.% were mixed to prepare a mixed impregnation liquid A.

(2) To the above mixed impregnation liquid A, 260 g of butyl octyl dithiophosphate was added to prepare a mixed impregnation liquid B.

(3) The mixed impregnating solution B was spray-impregnated on 500 g of the shaped activated carbon support by an equal volume impregnation method, then cured in air for 12 h, dried at 120 ° C for 4 h, and finally calcined at 600 ° C for 4 h to obtain a catalyst B.

Example 3 Preparation of Cu-Mn-Ce/Ceramic Catalyst

(1) 170 ml, 80 ml, and 30 ml of Cu(NO ₃ ) ₂ , Mn(NO ₃ ) ₂ , and Ce(NO ₃ ) ₃ solutions each having a metal ion concentration of 6 wt.% were mixed to prepare a mixed impregnation liquid A.

(2) To the above mixed impregnation liquid A, 200 g of tetradecyltributylammonium chloride was added to prepare a mixed impregnation liquid B.

(3) The above mixed impregnation liquid B and 500 g of the ceramic raw material were uniformly mixed, and then subjected to rolling granulation, and the granulation diameter was controlled.

(4) The pellet obtained in the step (3) is sealed and cured for 8 hours, and then dried at 120 ° C. 5h, finally calcined at 500 ° C for 5h to obtain catalyst C.

Example 4 Preparation of Mn-Fe-Ni-La/Alumina Catalyst

(1) Prepare Mn(NO ₃ ) ₂ , Fe(NO ₃ ) ₃ , Ni(NO ₃ ) ₂ , La(NO ₃ ) ₃ solution 150ml, 30ml, 30ml and 20ml with metal ion concentration of 8wt.% respectively. Mix the impregnation liquid A.

(2) To the mixed impregnation liquid A, 100 g of tetradecyldimethylbenzylammonium chloride was added to prepare a mixed impregnation liquid B.

(3) The above mixed impregnating solution B was spray-impregnated on 500 g of the shaped alumina carrier by an equal volume impregnation method, then maintained in air for 16 h, dried at 100 ° C for 5 h, and finally calcined at 400 ° C for 4 h to obtain a catalyst D.

The performance of the catalyst is evaluated below:

The catalyst prepared in Examples 1-4 and the commercially available, industrially used catalysts using alumina and activated carbon as supports and transition metals as active components (catalyst numbers E and F, respectively) were used for ozone ozone. Catalytic oxidation test evaluation, test conditions and test results are as follows:

Test conditions: The catalyst of the present invention was used in a fixed bed reactor to treat wastewater. The wastewater is reverse osmosis concentrated water. It is taken from the reverse osmosis unit of a petrochemical recycling unit of a petrochemical company of PetroChina. The composition of the wastewater is complex and contains high-level aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, polycyclic aromatic compounds and other organic pollutants that are difficult to biodegrade. The COD has a mass concentration of about 200 mg/L, a pH of 7.5-8.5, and a chloride ion mass concentration of about 2500 mg/L.

The catalyst bed volume is 377ml, the wastewater volumetric space velocity is 2h ^-1 (ie, the residence time is 30min), the O ₃ concentration is 8.1mg / L, the O ₃ volume flow rate is 80L / h; continuous operation at room temperature for 3h, 4h and At 5 h, the COD removal rate and BOD/COD ratio of the reverse osmosis concentrated water are listed in Table-1.

Table-1 Test Results of Catalyst Treatment of Reverse Osmosis Concentrated Water Performance

The ozone catalytic oxidation catalyst for wastewater treatment provided by the present invention and a preparation method thereof are described in detail above. The principles and embodiments of the present invention have been described with reference to specific examples, and the description of the above embodiments is only to assist in understanding the method of the present invention and its core idea. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

Claims

An ozone catalytic oxidation catalyst for wastewater treatment, characterized by comprising an active component, an auxiliary agent and a carrier; wherein the active component is a transition metal oxide, and the auxiliary agent is an alkali metal oxide or an alkaline earth metal An oxide or a lanthanide metal oxide; the support is alumina, activated carbon or ceramsite.
The ozone catalytic oxidation catalyst for wastewater treatment according to claim 1, wherein the active component is one or more transition metals selected from the group consisting of titanium, manganese, iron, cobalt, nickel, copper, and zinc. Oxide.
The ozone catalytic oxidation catalyst for wastewater treatment according to claim 1, wherein the auxiliary agent is one or more alkali metal oxides selected from the group consisting of sodium, potassium, magnesium, calcium, strontium, barium, An alkaline earth metal oxide or a lanthanide metal oxide.
The ozone catalytic oxidation catalyst for wastewater treatment according to claim 1, wherein the active component is 1.0% to 15% by mass, and the auxiliary agent is 0.1% to 1.0%, and the balance is Carrier.
A method for preparing an ozone catalytic oxidation catalyst for wastewater treatment, characterized in that a precursor compound of an active component and a precursor compound of an auxiliary agent are supported on a carrier by dipping or dry mixing, and are maintained and dried. Prepared after calcination; the precursor compound of the active component is a salt compound of a transition metal; the precursor compound of the auxiliary is an alkali metal salt compound, an alkaline earth metal salt compound or a lanthanoid metal a salt compound; the carrier is alumina, activated carbon or ceramsite.
The method for preparing an ozone catalytic oxidation catalyst for wastewater treatment according to claim 5, which comprises:

The precursor compound of the active component and the precursor compound of the auxiliary agent are formulated into a mixed impregnation liquid A;

Adding a dispersing agent to the mixed impregnation liquid A to prepare a mixed impregnation liquid B;

The mixed impregnation liquid B is supported on a carrier, and then the catalyst is obtained by curing, drying, and calcining.
The ozone catalytic oxidation catalyst for wastewater treatment according to claim 6 The preparation method is characterized in that, when the mixed impregnation liquid A is prepared, the precursor compound of the active component and the precursor compound of the auxiliary component are respectively the precursor compound solution of the active component and the precursor compound solution of the auxiliary component Forming the mixed impregnation liquid A, the precursor compound of the active component in the precursor compound solution has a metal ion mass concentration of 1% to 15%; the precursor compound solution of the auxiliary agent is assisted The precursor compound of the agent has a metal ion mass concentration of from 1% to 15%.
The method of preparing an ozone catalytic oxidation catalyst for wastewater treatment according to claim 6, wherein the dispersant is a compound of phosphorus, silicon, boron, nitrogen, sulfur or halogen.
The method for producing an ozone catalytic oxidation catalyst for wastewater treatment according to claim 6, wherein the dispersant is added in an amount of from 100 to 1000 g/L.
The method for preparing an ozone catalytic oxidation catalyst for wastewater treatment according to claim 6, wherein the calcination temperature is 400-800 ° C and the calcination time is 2-6 h.