CN109012679B - Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof - Google Patents

Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN109012679B
CN109012679B CN201811152438.6A CN201811152438A CN109012679B CN 109012679 B CN109012679 B CN 109012679B CN 201811152438 A CN201811152438 A CN 201811152438A CN 109012679 B CN109012679 B CN 109012679B
Authority
CN
China
Prior art keywords
solution
catalyst
based catalyst
stirring
soluble
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.)
Active
Application number
CN201811152438.6A
Other languages
Chinese (zh)
Other versions
CN109012679A (en
Inventor
王秀云
张凯
曹彦宁
肖益鸿
江莉龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou University
Original Assignee
Fuzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Priority to CN201811152438.6A priority Critical patent/CN109012679B/en
Publication of CN109012679A publication Critical patent/CN109012679A/en
Application granted granted Critical
Publication of CN109012679B publication Critical patent/CN109012679B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a high-efficiency and low-temperature Fe-based catalyst and a preparation method and application thereof, wherein the Fe-based catalyst is prepared by taking soluble ferric salt and soluble titanium salt or soluble zinc salt as raw materials through a coprecipitation method; wherein the mol ratio of the soluble ferric salt to the soluble titanium salt or the soluble zinc salt is (1:0) - (7: 1). The Fe-based catalyst prepared by the invention has high toluene low-temperature conversion efficiency, wherein Ti-alpha-Fe2O3The catalytic conversion rate of the catalyst at 321 ℃ in toluene reaches 90%, and the catalyst has extremely high water-resistant thermal stability and obvious industrial application value.

Description

Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of catalyst material preparation, and particularly relates to a high-efficiency and low-temperature Fe-based catalyst, and a preparation method and application thereof.
Background
With the development of economy and the increasing living standard of people, environmental problems are more and more valued by people. Volatile Organic Compounds (VOCs) derived from natural sources such as volcanic eruption, plant release and forest fire and artificial sources such as industrial production, vehicle exhaust emission, agricultural production and human daily life are one of main pollutants in the atmosphere, can cause environmental problems such as the formation of smoke and greenhouse effect and the damage of stratospheric ozone, can also stimulate eyes and upper respiratory systems of people, damage central nerves and hematopoietic tissues, and cause great harm to human health. In order to improve air quality, conventional control processes including adsorption, membrane separation and condensation, and emerging technologies such as photocatalysis, plasma catalysis, thermal oxidation and catalytic oxidation have been proposed to effectively cope with air pollution problems. Among these technologies, the catalytic oxidation technology is considered as one of the most effective removal routes of volatile organic compounds because of its low light-off temperature, simple equipment, no secondary pollution, and high catalytic oxidation efficiency.
Noble metal catalysts can exhibit excellent catalytic performance at relatively low temperatures, but generally require high noble metal loading, and because noble metals such as Au, Pd, and Pt are expensive and the noble metal catalysts are easily sintered at high temperatures, the practical application of noble metal catalysts in toluene catalytic combustion is greatly limited. One promising alternative to noble metal-based catalysts is the transition metal oxides (including Fe)2O3，TiO2ZnO, etc.) which have been studied by numerous researchers because of their low cost, ready availability of raw materials, and excellent toluene combustion performance.
Disclosure of Invention
The invention aims to provide a high-efficiency Fe-based catalyst for low-temperature catalytic combustion of hydrocarbons and a preparation method thereof, which can solve the problems of high cost, complex operation and the like commonly existing in the catalytic combustion process of hydrocarbons.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-temperature high-efficiency Fe-based catalyst is prepared by taking soluble ferric salt and soluble titanium salt or soluble zinc salt as raw materials and preparing the Fe-based catalyst by a coprecipitation method; wherein the mol ratio of the soluble ferric salt to the soluble titanium salt or the soluble zinc salt is (1:0) - (7: 1).
The soluble ferric salt is FeCl3、Fe(NO3)3、Fe2(SO4)3、FeCl2、Fe(NO3)2、FeSO4Any one or more of them.
The soluble titanium salt is TiCl4、Ti(NO3)4、Ti(SO4)2Any one or more of them.
The soluble zinc salt is ZnCl2、Zn(NO3)2、ZnSO4Any one or more of them.
The preparation method of the Fe-based catalyst comprises the following steps:
(1) respectively weighing soluble ferric salt, soluble titanium salt or soluble zinc salt according to a molar ratio, adding water to prepare a mixed salt solution, and then adding 1 mol/L hydrochloric acid solution to adjust the pH value to be less than 1;
(2) dropwise adding 2.5-25 wt% ammonia water solution into the mixed salt solution obtained in the step (1) at a speed of 3-8 mL/min under the stirring condition, adjusting the pH value to 9-13, continuously stirring for 1-5 h after dropwise adding is finished, and then standing for 12-36 h;
(3) and centrifuging the obtained product, washing to be neutral, drying at 70-130 ℃ for 6-18 h, heating to 500-700 ℃ at the speed of 3-4 ℃/min, and roasting for 3-5 h to obtain the Fe-based catalyst.
The Fe-based catalyst obtained by the invention can be used for low-temperature catalytic combustion of low-concentration hydrocarbons, including hydrocarbon tail gas discharged in association with oil fields.
The invention has the following remarkable advantages:
(1) the invention can prepare the alpha-Fe by a coprecipitation method2O3、Zn-α-Fe2O3Or Ti-alpha-Fe2O3The catalyst obtained by the method has high catalytic oxidation activity in a wide temperature range.
(2) The invention firstly applies the transition metal iron-based catalyst to the field of catalytic oxidation of hydrocarbons, in particular to the catalytic oxidation of toluene, has good water resistance and stability in the catalytic oxidation reaction of toluene, and greatly widens the application field of the transition metal iron-based catalyst.
(3) The catalyst provided by the invention has better catalytic effect than the traditional toluene catalytic oxidation catalyst, and has the advantages of simple preparation process, convenient operation, low cost, high toluene conversion rate and obvious industrial application value.
Drawings
FIG. 1 is an XRD pattern of the catalysts obtained in examples 1-3.
FIG. 2 shows Ti-. alpha. -Fe obtained in example 32O3Formazan at 500 ℃ in the presence of 3% VOL waterBenzene conversion.
FIG. 3 shows the toluene conversion of the catalysts obtained in examples 1 to 3 and comparative example at different temperature points.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
1) 13.515g (0.05 mol) FeCl was weighed3·6H2O and 6.951g (0.025 mol) FeSO4·7H2O, dissolved in 500mL of deionized water, and the pH is adjusted to 1 mol/L with HCl solution<1, rapidly stirring for 15 minutes to form a mixed solution a;
2) measuring 10 ml of 25 wt% ammonia water, dissolving in 100 ml of water, and quickly stirring for 15 minutes to form an ammonia water solution b;
3) under the condition of stirring, slowly dropwise adding the ammonia water solution b into the mixed solution a at the speed of 5mL/min by using a peristaltic pump until the pH of the solution is about 9-13, stopping dropwise adding, continuously stirring for 3 h, and standing for 36 h;
4) centrifuging and washing the obtained product to neutrality, drying at 70 ℃ for 18 h, placing in a muffle furnace, heating to 550 ℃ at the speed of 3 ℃/min, and roasting at high temperature for 4h to obtain alpha-Fe2O3A catalyst.
Example 2
1) 13.515g (0.05 mol) FeCl was weighed3·6H2O and 7.189g (0.045 mol) ZnSO4Dissolved in 500mL of deionized water, and the pH value is adjusted to the value of 1 mol/L by HCl solution<1, rapidly stirring for 15 minutes to form a mixed solution a;
2) measuring 10 ml of 25 wt% ammonia water, dissolving in 100 ml of water, and quickly stirring for 15 minutes to form an ammonia water solution b;
3) under the condition of stirring, slowly dropwise adding the ammonia water solution b into the mixed solution a at the speed of 5mL/min by using a peristaltic pump until the pH of the solution is about 9-13, stopping dropwise adding, continuously stirring for 3 h, and standing for 36 h;
4) isolating the obtained productWashing to neutrality, drying at 70 deg.C for 18 h, placing in a muffle furnace, heating to 550 deg.C at 3 deg.C/min, and high-temperature roasting for 4h to obtain Zn-alpha-Fe2O3A catalyst.
Example 3
1) 16.217g (0.06 mol) FeCl was weighed3·6H2O、47.263g（0.17mol）FeSO4·7H2O and 16.800g (0.07 mol) Ti (SO)4)2Dissolved in 500mL of deionized water, and the pH value is adjusted to the value of 1 mol/L by HCl solution<1, rapidly stirring for 15 minutes to form a mixed solution a;
2) measuring 10 ml of 25 wt% ammonia water, dissolving in 100 ml of water, and quickly stirring for 15 minutes to form an ammonia water solution b;
3) under the condition of stirring, slowly dropwise adding the ammonia water solution b into the mixed solution a at the speed of 5mL/min by using a peristaltic pump until the pH of the solution is about 9-13, stopping dropwise adding, continuously stirring for 3 h, and standing for 36 h;
4) centrifuging and washing the obtained product to neutrality, drying at 70 ℃ for 18 h, placing in a muffle furnace, heating to 550 ℃ at the speed of 3 ℃/min, and roasting at high temperature for 4h to obtain Ti-alpha-Fe2O3A catalyst.
1. The measurement is carried out by adopting an X' Pert PRO type X-ray powder diffractometer of Panalytical company in the Netherlands, wherein a radiation source is a Cu target, the test precision is 0.001 degree/step, the incident wavelength is 0.1790nm, the pipe flow is 40mA, the pipe pressure is 40kV, the scanning step length is 0.02 degree, the scanning speed is 0.60sec/step, and the scanning time of each step is 10 s. FIG. 1 is an XRD pattern of the catalysts obtained in examples 1-3.
It can be seen from the figure that alpha-Fe is synthesized2O3(ii) a After Ti is added, the sharpness of the hematite peak type is weakened, which indicates that Ti is more uniformly dispersed in the hematite structure; while after the addition of Zn, ZnFe appears2O4Characteristic peak of (2).
2. Toluene conversion was measured on a continuous flow mini-fixed bed using 200 mg of the catalyst of example 3 and a mass space velocity of 40000 mL/(g.h), the toluene concentration change in the off-gas was measured by gas chromatography, and the reaction gas composition was: 1000 ppm toluene, balance air. 3 percent of VOL water is introduced in the reaction process. Determination of Ti-alpha-Fe at 500 deg.C2O3The catalyst has toluene conversion effect, and the test results are shown in FIG. 2.
As can be seen from FIG. 2, Ti-. alpha. -Fe2O3Has better thermal stability and water-resistant stability at 500 ℃.
Comparative example
1) 13.515g (0.05 mol) FeCl was weighed3·6H2O and 6.951g (0.025 mol) FeSO4·7H2O, dissolved in 500mL of deionized water, and the pH is adjusted to 1 mol/L with HCl solution<1, rapidly stirring for 15 minutes to form a mixed solution a;
2) measuring 10 ml of 25 wt% ammonia water, dissolving in 100 ml of water, and quickly stirring for 15 minutes to form an ammonia water solution b;
3) under the condition of stirring, slowly dropwise adding the ammonia water solution b into the mixed solution a at the speed of 5mL/min by using a peristaltic pump until the pH of the solution is about 9-13, stopping dropwise adding, continuously stirring for 3 h, and standing for 36 h;
4) centrifuging and washing the obtained product to neutrality, drying at 70 ℃ for 18 h, placing in a muffle furnace, heating to 350 ℃ at the speed of 3 ℃/min, and roasting at high temperature for 4h to obtain gamma-Fe2O3A catalyst.
Using 200 mg of each of the catalysts obtained in examples 1 to 3 and comparative example, respectively, and a mass space velocity of 40000 mL/(g.h), toluene conversion was measured on a continuous flow mini-fixed bed, and the change in the toluene concentration in the off-gas was measured by gas chromatography, and the reaction gas composition was: 1000 ppm toluene, the remainder being air; the flow rate of the raw material gas is 130--1(ii) a The inner diameter of the reaction tube was 5 mm. The effect of the catalyst on toluene conversion was determined at 180 ℃ and 390 ℃ and the results are shown in FIG. 3.
As can be seen from FIG. 3, with γ -Fe2O3In comparison, the catalysts obtained in examples 1 to 3 exhibited better activity for the low-temperature conversion of toluene.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (1)

1. A preparation method of Fe-based catalyst for catalyzing low-concentration hydrocarbon combustion is characterized by comprising the following steps: the method comprises the following steps:
1) weighing 0.06mol of FeCl3·6H2O、0.17mol FeSO4·7H2O and 0.07mol of Ti (SO)4)2Dissolved in 500mL of deionized water, and the pH value is adjusted to be 1 mol/L HCl solution<1, rapidly stirring for 15 minutes to form a mixed solution a;
2) measuring 10 ml of 25 wt% ammonia water, dissolving in 100 ml of water, and quickly stirring for 15 minutes to form an ammonia water solution b;
3) under the condition of stirring, slowly dropwise adding the ammonia water solution b into the mixed solution a at the speed of 5mL/min by using a peristaltic pump until the pH value of the solution is 9-13, stopping dropwise adding, continuously stirring for 3 h, and standing for 36 h;
4) centrifuging and washing the obtained product to neutrality, drying at 70 ℃ for 18 h, placing in a muffle furnace, heating to 550 ℃ at the speed of 3 ℃/min, and roasting at high temperature for 4h to obtain Ti-alpha-Fe2O3A catalyst.
CN201811152438.6A 2018-09-29 2018-09-29 Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof Active CN109012679B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811152438.6A CN109012679B (en) 2018-09-29 2018-09-29 Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811152438.6A CN109012679B (en) 2018-09-29 2018-09-29 Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109012679A CN109012679A (en) 2018-12-18
CN109012679B true CN109012679B (en) 2021-09-24

Family

ID=64615492

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811152438.6A Active CN109012679B (en) 2018-09-29 2018-09-29 Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109012679B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114405508B (en) * 2022-03-10 2023-10-10 福州大学 Ti-doped Fe oxide residual oil suspension bed hydrocracking catalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011230087A (en) * 2010-04-30 2011-11-17 National Institute Of Advanced Industrial Science & Technology Decomposition catalyst and decomposition method of organic compound
CN104722304A (en) * 2012-01-16 2015-06-24 南开大学 Mesoporous calcium doped iron oxide composite catalyst for catalytic oxidation of polychlorinated aromatic hydrocarbon
CN105582960A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Catalyst used for producing butadiene through butene oxidative dehydrogenation, and application method thereof
CN106622241A (en) * 2017-01-06 2017-05-10 中国石油大学(华东) Nano spinel type catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011230087A (en) * 2010-04-30 2011-11-17 National Institute Of Advanced Industrial Science & Technology Decomposition catalyst and decomposition method of organic compound
CN104722304A (en) * 2012-01-16 2015-06-24 南开大学 Mesoporous calcium doped iron oxide composite catalyst for catalytic oxidation of polychlorinated aromatic hydrocarbon
CN105582960A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Catalyst used for producing butadiene through butene oxidative dehydrogenation, and application method thereof
CN106622241A (en) * 2017-01-06 2017-05-10 中国石油大学(华东) Nano spinel type catalyst and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Combustion of Toluene over Titanium(IV) Oxide Catalyst;Byonggu AN et al.;《Journal of the Japan Petroleum Institute》;20071231;第50卷(第5期);第283-286页 *
Template-assisted hydrothernally synthesized iron-titanium binary oxides and their application as catalysts for ethyl acetate oxidation;Tanya Tsoncheva et al.;《Applied Catalysis A:General》;20160914;第528卷;第24-35页 *

Also Published As

Publication number Publication date
CN109012679A (en) 2018-12-18

Similar Documents

Publication Publication Date Title
CN108325549A (en) It is a kind of for the transition metal of purifying formaldehyde and nitrogen co-doped carbon composite and preparation method thereof
CN102962050B (en) Tin-based composite oxide catalyst for flue gas denitrification and preparation method of catalyst
CN111013602B (en) Molding Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof
CN105289644B (en) A kind of flat sulfur resistive low temperature SCR denitration catalyst and preparation method thereof
CN108435189B (en) Samarium-doped iron-based denitration catalyst with water resistance and sulfur resistance and preparation method thereof
EP0457480B1 (en) Catalytic reduction
CN106513050B (en) A kind of preparation method of CdS/MIL-53 (Fe) visible light catalyst
CN111545192A (en) MOFs-derived perovskite catalyst, preparation method thereof and application of MOFs-derived perovskite catalyst in catalytic degradation of organic pollutants
CN110773151B (en) Porous bixbyite Mn loaded with diatomite2O3Catalyst, preparation method and application thereof
CN108620113B (en) Preparation method of nitrogen-doped carbon-cerium composite nanosheet
CN108940266A (en) A kind of low-temperature SCR catalyst and preparation method thereof
CN107362800A (en) A kind of VOCs eliminates catalyst and preparation method thereof
CN109012679B (en) Low-temperature high-efficiency Fe-based catalyst and preparation method and application thereof
CN107899583A (en) It is a kind of to prepare catalyst of ethanol and preparation method thereof for methyl methanol syngas
CN110665513B (en) Modified manganese oxide catalyst and preparation method and application thereof
CN111141783B (en) Tin dioxide nanoparticle gas-sensitive material and preparation method and application thereof
CN108993516A (en) It is a kind of using NiTi hydrotalcite as composite oxide catalysts of presoma and its preparation method and application
CN112844374A (en) Mn-Ce-Ti oxide aerogel denitration catalyst and preparation method and application thereof
CN112264016A (en) High-defect cobaltosic oxide catalyst for catalytic oxidation of formaldehyde and preparation method and application thereof
CN111889100A (en) Cryptomelane type mixed manganese oxide catalyst for removing soot of diesel vehicle through oxidation
JP2002355558A (en) Method for oxidation removal of formaldehyde
CN110252317B (en) Ce-Fe-based catalyst for efficiently removing nitrogen oxides at low temperature
CN111672536A (en) Noble metal catalyst for formaldehyde purification and preparation method thereof
CN105817227A (en) Preparation method of nano nickel oxide used for propane catalytic combustion reaction
CN114225941B (en) SCR catalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant