CN116713031A - Recyclable magnetic thermocatalytic material and preparation method and application thereof - Google Patents

Recyclable magnetic thermocatalytic material and preparation method and application thereof Download PDF

Info

Publication number
CN116713031A
CN116713031A CN202310413793.9A CN202310413793A CN116713031A CN 116713031 A CN116713031 A CN 116713031A CN 202310413793 A CN202310413793 A CN 202310413793A CN 116713031 A CN116713031 A CN 116713031A
Authority
CN
China
Prior art keywords
cofe
sio
magnetic
core
thermocatalytic
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.)
Pending
Application number
CN202310413793.9A
Other languages
Chinese (zh)
Inventor
管蓓
陈英文
徐颖彤
高宁
刘济宁
沈岳松
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.)
Nanjing Tech University
Original Assignee
Nanjing Tech 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 Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN202310413793.9A priority Critical patent/CN116713031A/en
Publication of CN116713031A publication Critical patent/CN116713031A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Thermal Sciences (AREA)
  • Composite Materials (AREA)
  • Hydrology & Water Resources (AREA)
  • Manufacturing & Machinery (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a recyclable magnetic thermocatalytic material, a preparation method and application thereof, wherein the preparation process comprises the following steps: (1) General purpose medicinePreparation of spinel-structured CoFe by hydrothermal method 2 O 4 As the center of the magnetic core-shell structure; (2) CoFe is prepared by using tetraethoxysilane as a material through a St foster method 2 O 4 @SiO 2 Core-shell structure in which SiO 2 For CoFe at high temperature 2 O 4 The magnetism has a protective effect; (3) CoFe is to be CoFe 2 O 4 @SiO 2 Dissolving in precursor solution of active component, calcining to obtain CoFe 2 O 4 Is magnetic core-shell SiO 2 The core-shell structure catalytic material which is a protective layer and has the active component of a catalytic layer has great potential in the actual pyrolysis process of the oil-containing sludge.

Description

Recyclable magnetic thermocatalytic material and preparation method and application thereof
Technical Field
The application relates to the technical field of catalytic pyrolysis of oily sludge, in particular to a recyclable magnetic thermocatalytic material, a preparation method and application thereof.
Background
In the treatment of hazardous wastes such as oil-containing sludge brought by the development of petroleum industry, the traditional pyrolysis catalyst is expanded to be recoverable after high-temperature pyrolysis, and the adhesion of pyrolytic carbon deposit is reduced. In particular, the utilization of high temperature magnetically active materials provides unique functionality for the development of high performance pyrolysis catalysts, potentially reducing operating costs.
The application patent with the patent application number of CN200910087741.7 in the prior art provides a preparation method of a magnetic-supported titanium dioxide photocatalyst taking micron-sized nickel ferrite as a carrier. Adding ferrous sulfate solution and oxalic acid solution into nickel sulfate solution to react to obtain oxalate mixture precipitate of nickel oxalate and ferrous oxalate, and roasting to obtain micron-sized nickel ferrite powder; adding the titanium sulfate solution into the suspension of the micron-sized nickel ferrite powder, and precipitating and crystallizing titanium ions on suspended particles in the suspension to form a coating layer, thereby obtaining the nickel ferrite-based magnetically supported titanium dioxide photocatalyst product. The magnetic supported photocatalyst prepared by the method has good dispersibility, particle size of about 5 mu m, titanium dioxide is obviously coated on the surface of nickel ferrite to form a core/shell structure, the coating quantity is large and adjustable, the distribution is uniform, and the specific surface area reaches 90-110m 2 /g, with strong soft magneticThe characteristics of the catalyst can be quickly recovered in aqueous solution, has higher catalytic activity, and can completely degrade organic wastewater. The preparation process is simple, the cost is low, and the catalyst is easy to produce in large scale, but the catalyst prepared by the application can not be used for catalytic pyrolysis of the oily sludge and can not be recycled.
Therefore, it is highly desirable to invent a novel economic, environment-friendly and efficient pyrolysis catalytic material for oil-containing sludge, which can effectively reduce pyrolysis activation energy, improve product quality and yield, and can effectively recover and have regeneration activity.
Disclosure of Invention
The application provides a recoverable magnetic thermocatalytic material, a preparation method and application thereof, wherein the catalyst uses CoFe 2 O 4 Is a shell with a core-shell structure, siO 2 Is a coating layer, the active component is a catalytic layer, and the CoFe is prepared 2 O 4 @SiO 2 Catalytic material with a @ RC core-shell structure. The material can improve the yield and quality of pyrolysis oil in the catalytic pyrolysis process of the oily sludge, reduce the reaction activation energy, has high-temperature recoverability, effectively reduces the serious deactivation phenomenon of carbon deposition of a conventional catalyst, improves the activity of the catalyst, can be regenerated and recycled by a catalyst recovery oxidation method, and has the advantages of small secondary pollution and low economic cost.
The application discloses a recoverable magnetic thermocatalytic material, wherein the catalyst is CoFe 2 O 4 @SiO 2 Catalytic material with @ RC core-shell structure and CoFe 2 O 4 Is a shell with a core-shell structure, siO 2 The active component is a catalytic layer.
Preferably, the catalytic layer is prepared from an active component synthetic solution, and the active component synthetic solution contains any one or more of ZSM-5, HZSM-5, MCM-41, metal oxide and metal salt compounds.
The application also discloses a preparation method of the recyclable magnetic thermocatalytic material, which comprises the following steps:
(1) Preparation of CoFe by hydrothermal method 2 O 4 A crystal;
(2) The CoFe obtained in the step (1) is treated 2 O 4 The crystal adopts St-pad method loaded SiO 2 Preparation of CoFe 2 O 4 @SiO 2 Core-shell structured particles;
(3) The CoFe obtained in the step (2) is treated 2 O 4 @SiO 2 The core-shell structure particles are immersed into the active component synthesis liquid to form CoFe 2 O 4 @SiO 2 An @ RC mixed solution;
(4) The CoFe obtained in the step (3) is treated 2 O 4 @SiO 2 Crystallizing the @ RC mixed solution to obtain CoFe 2 O 4 @SiO 2 The @ RC may recover the magnetic thermocatalytic material.
Preferably, coFe is prepared in step (1) 2 O 4 When in crystallization, ferric acetylacetonate and cobalt acetylacetonate are taken as materials, ferric acetylacetonate, cobalt acetylacetonate and 0.2g-0.3g octadecylamine with the molar ratio of 1:1-3 are dissolved, the mixture is put into a high-pressure reaction kettle for reaction, cooled after the reaction, and centrifuged repeatedly to obtain CoFe 2 O 4 Separating the solution and separating CoFe 2 O 4 Drying the separated solution and grinding the dried solution to powder to obtain CoFe 2 O 4 And (5) a crystal.
Specifically, in the step (1), the molar ratio of the ferric acetylacetonate to the cobalt acetylacetonate is any value in the range of 1:1-3, such as 1:1,1:2 and 1:3; the octadecylamine is used in an amount of any value in the range of 0.2g to 0.3g, such as 0.2g,0.25g,0.3g.
In any of the above embodiments, it is preferred that CoFe is prepared in step (1) 2 O 4 In the case of crystals, ferric chloride and cobalt chloride are used as raw materials.
In any of the above schemes, preferably, in the step (1), after ferric acetylacetonate, cobalt acetylacetonate and octadecylamine are dissolved, the mixture is put into a high-pressure reaction kettle to react at 180-220 ℃ for 12-36 h, cooled and repeatedly centrifuged by ethanol at 5000 rpm to obtain CoFe 2 O 4 Separating the solution and separating CoFe 2 O 4 Drying the separated solution at 100-120deg.C for 48 h, and grinding to obtain CoFe powder 2 O 4 And (5) a crystal.
Specifically, ferric acetylacetonate, cobalt acetylacetonate and octadecylamine are dissolved and then put into high-pressure reactionWhen the reaction is carried out in a reaction kettle, the reaction temperature is any value within the range of 180-220 ℃, such as 180 ℃,190 ℃,200 ℃,210 ℃ and 220 ℃; the reaction time is any value in the range of 12-36 h, such as 12h,15h,18h,20h,25h,28h,30h,36h; cooling to room temperature, repeatedly centrifuging with ethanol at 5000 rpm to obtain CoFe 2 O 4 Drying the separated solution at a temperature of any value within the range of 100-120deg.C, such as 100deg.C, 110deg.C, 115deg.C, 120deg.C, and drying time of 48 h, and grinding to powder.
In any of the above embodiments, it is preferred that CoFe is prepared in step (2) 2 O 4 @SiO 2 The core-shell structure particles comprise the following specific steps: the CoFe obtained in the step (1) is treated 2 O 4 Dispersing crystal and sodium dodecyl benzene sulfonate into deionized water, ultrasonic treating, adding ammonium hydroxide and tetraethoxysilane, stirring, washing and drying to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
In any of the above embodiments, it is preferable that in step (2), 0.05 g to 0.15 g CoFe is added 2 O 4 Dispersing the particles and 0.5g-1.5 g sodium dodecyl benzene sulfonate into 10-30ml deionized water to obtain a mixed solution, adding 60ml-100 ml ethanol into the mixed solution and carrying out ultrasonic treatment for 0.8-1.2h, adding 4-6ml ammonium hydroxide and 600 mu l-1000 mu l tetraethoxysilane under the condition of continuously stirring at room temperature, fully stirring the suspension for 9-11 h, washing with deionized water, and drying at 80-90 ℃ for 5.5h-6.5h to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
Specifically, coFe in step (2) 2 O 4 The amount of the particles is any value in the range of 0.05 g-0.15 g, such as 0.05 g,0.1 g,0.15 g; sodium dodecyl benzene sulfonate is used in an amount of any value in the range of 0.5g-1.5 g, such as 0.5g, 1g,1.5 g; adding 60ml-100 ml ethanol into the mixed solution, and performing ultrasonic treatment, wherein the ethanol dosage is any value in the range of 60ml-100 ml, such as 60ml,80ml and 100ml, and the ultrasonic treatment time is any value in the range of 0.8-1.2h, such as 0.8h,1h and 1.2h; ammonium hydroxide and tetraethoxysilane were added with continuous stirring at room temperature, ammonium hydroxide was usedThe amount is any value in the range of 4-6ml, such as 4ml,5ml,6ml, and the tetraethoxysilane amount is any value in the range of 600. Mu.l-1000. Mu.l, such as 600. Mu.l, 800. Mu.l, 1000. Mu.l.
In any of the above schemes, it is preferable that the ammonium hydroxide in step (2) is an aqueous solution having a mass fraction of 10% -40%.
The ammonium hydroxide can be 10% -40% of aqueous solution by mass, such as 10%,20%,30% and 40%.
In any of the above embodiments, it is preferable that in the step (3), coFe prepared in the step (2) of 1 to 3g is added 2 O 4 @SiO 2 Adding the core-shell structure particles into 15-25 ml active component synthetic liquid, regulating pH to neutrality, and forming CoFe 2 O 4 @SiO 2 Mixed solution @ RC.
Specifically, coFe prepared in the step (2) 2 O 4 @SiO 2 The dosage of the core-shell structure particles is any value in the range of 1g-3 g, such as 1g,2g and 3g; the amount of the active ingredient combination is any value within the range of 15 to 25 and ml, such as 15ml,20ml and 25ml.
In any of the above embodiments, preferably, in the step (3), the active ingredient synthesis liquid comprises any one or more of ZSM-5 synthesis liquid, HZSM-5 synthesis liquid, MCM-41 synthesis liquid, metal oxide and metal salt compound.
In any of the above embodiments, the metal oxide is preferably CaO, mgO, fe 2 O 3 At least one of the metal salt compounds is KOH, znCl 2 、K 2 CO 3 At least one of them.
In any of the above schemes, preferably, the preparation method of the ZSM-5 synthetic solution comprises the following steps: solution A was prepared with TEOS (tetraethoxysilane), TPAOH (tetrapropylammonium hydroxide) and deionized water, with Al (NO) 3 ) 3 ·9H 2 O, naOH and deionized water to prepare solution B; then the solution A is heated and hydrolyzed by a water bath method, and the solution B is added into the solution A to form the catalyst with the molar ratio of n (Na 2 O)：n(Al 2 O 3 )：n(SiO 2 )：n(TPAOH)：n(H 2 O) =0.05: 0.0125:1:0.25: 60.
In any of the above schemes, preferably, the preparation method of the HZSM-5 synthetic solution comprises the following steps: dissolving TPABr in deionized water, stirring, adding NH 3 ·H 2 O, further adding Al (NO) 3 ) 3 ·9H 2 O and TEOS are stirred to form a mixture with a molar ratio n (SiO 2 )：n(Al 2 O 3 )：n(TPABr)：n(NH 3 ·9H 2 O)：n(H 2 O) =100: 1:10:150:1100 HZSM-5 synthesis solution.
In any of the above schemes, preferably, the preparation method of the MCM-41 synthetic solution comprises the following steps: using CTAB (cetyl trimethyl ammonium bromide) as a template agent, and mixing NaOH and silica sol (containing 40% of SiO by mass percent) 2 ) Stirring, adding CTAB and deionized water, and stirring to obtain a mixture with a molar ratio of n (SiO 2 )：n(Na 2 O)：n(CTAB)：n(H 2 O) =1: 0.25:0.25:100 MCM-41 synthesis solution.
In any of the above embodiments, it is preferable that in the step (4), coFe prepared in the step (3) is used 2 O 4 @SiO 2 The crystallization treatment method of the @ RC mixed solution comprises the following steps: coFe is to be CoFe 2 O 4 @SiO 2 Reacting the @ RC mixed solution in a baking oven, cooling, washing to neutrality, drying, and roasting to obtain CoFe 2 O 4 @SiO 2 The @ RC may recover the magnetic thermocatalytic material.
In any of the above embodiments, it is preferable that in the step (4), coFe 2 O 4 @SiO 2 When the mixed solution @ RC is crystallized in an oven, the temperature is set to be 130-190 ℃ and the reaction time is 24 h-72 h.
CoFe 2 O 4 @SiO 2 When the mixed solution of @ RC is crystallized in an oven, the temperature is any value in the range of 130-190 ℃, such as 130 ℃,150 ℃,180 ℃,190 ℃ and the reaction time is any value in the range of 24 h-72 h, such as 24 h,30h,40h,50h,60 h,72 h.
In any of the above embodiments, it is preferable that in the step (4), coFe 2 O 4 @SiO 2 Reacting the @ RC mixed solution in an oven, cooling, washing to neutrality, drying, roasting at 100-120deg.C for 5.5-6.5 hrRoasting at 520-570 deg.c to 3.5-4.5. 4.5h. And during drying and roasting, the temperature and time are sufficient enough to dry and burn out impurities.
In this step, the drying temperature may be specifically any value in the range of 100 to 120 ℃, such as 100 ℃,110 ℃,120 ℃; the drying time is any value in the range of 5.5-6.5h, such as 5.5h,6h,6.5h; the roasting temperature is any value in the range of 520-570 ℃, such as 520 ℃,550 ℃,570 ℃ and the roasting time is any value in the range of 3.5-4.5 h, such as 3.5h,4h and 4.5h.
The application also provides application of the recyclable magnetic thermocatalytic material obtained by the preparation method in pyrolysis of oily sludge and improvement of pyrolysis oil yield and quality. The recyclable magnetic thermocatalytic material can reduce the activation energy.
The application also provides a recovery method of the recoverable magnetic thermocatalytic material, which comprises the following steps: the recyclable magnetic thermocatalytic material (catalyst) can be recycled through a magnetic separation method, specifically, the reacted mixture is paved on sample paper, and the magnetic recyclable magnetic thermocatalytic material is absorbed by a magnet to be separated from pyrolysis residues; the recovered recoverable magnetic thermocatalyst material is burned for 90 min at 500 ℃ under the atmosphere of 150 mL/min oxygen flow, and the regenerated recoverable magnetic thermocatalyst material (regenerated catalyst) is obtained. The recyclable magnetic thermocatalytic material after pyrolysis is recovered by a magnetic separation method, and is subjected to oxidation method regeneration, and the recyclable magnetic thermocatalytic material still has catalytic effect on pyrolysis of oil-containing sludge. The material can improve the yield and quality of pyrolysis oil in the catalytic pyrolysis process of oily sludge, reduce the reaction activation energy, has high-temperature recoverability, can effectively reduce the serious deactivation phenomenon of conventional catalyst carbon deposition, improves the catalyst activity, can be regenerated and recycled by a catalyst recovery oxidation method, and has the advantages of small secondary pollution and low economic cost.
Advantageous effects
(1) The application discloses a recyclable magnetic thermocatalytic material, a preparation method and application thereof, wherein the preparation process comprises the following steps: (1) Fe (acac) 3 And Co (acac) 3 Preparation of spinel-structured CoF by hydrothermal methode 2 O 4 As the center of the magnetic core-shell structure; (2) CoFe is prepared by using tetraethoxysilane as a material through a St foster method 2 O 4 @SiO 2 Core-shell structured particles, wherein SiO 2 For CoFe at high temperature 2 O 4 The magnetism has a protective effect; (3) CoFe is to be CoFe 2 O 4 @SiO 2 The core-shell structure particles are dissolved into active component precursor solutions (ZSM-5, HZSM-5, MCM-41, metal oxide, metal salt compound and the like) and are roasted to finally form the CoFe 2 O 4 Is magnetic core-shell SiO 2 Is a core-shell structure catalytic material with a protective layer and active components (ZSM-5, HZSM-5, MCM-41, metal oxide, metal salt compound and the like) as catalytic layers. Because the magnetic core-shell has magnetism at 600 ℃, compared with the common oily sludge pyrolysis catalytic material, the magnetic core-shell can be recycled, and the magnetic separation recovery rate reaches 95%; the catalytic layer promotes the viscosity reduction of heavy oil, improves the yield and quality of pyrolysis oil, and has great potential in the actual pyrolysis process of oil-containing sludge.
(2) The core-shell structure material synthesized by the application realizes different pore channel structures on the catalyst, optimizes the pore channel structures, has more active sites, and can further promote the pyrolysis of the oil-containing sludge and improve the yield and quality of pyrolysis oil compared with the traditional pyrolysis catalytic material.
(3) The application uses CoFe 2 O 4 The high-temperature magnetic material is a shell with a core-shell structure, has the advantages of reversible magnetism, high saturation magnetization, low cost and the like, has a crystal structure which is favorable for catalytic reaction in the catalytic process, and can be recycled through a magnetic separation method compared with the traditional oily sludge pyrolysis catalyst, so that the problem that the traditional catalyst is difficult to separate from the oily sludge is solved, secondary pollution is reduced, and the running cost is potentially reduced.
（4）SiO 2 The coating layer can not only effectively control the thickness of the shell layer, but also ensure that the magnetic nano particles show good dispersibility. In the high-temperature pyrolysis process of the oily sludge, carbon deposit generated can be attached to the catalyst, so that the catalyst is deactivated, the service life is shortened, and compared with the traditional catalyst, the catalyst has the advantages of high-temperature pyrolysis efficiency, low cost and low costSiO of the catalyst 2 The coating layer can effectively reduce the adhesion of carbon deposition of the catalyst, prolong the service life of the catalyst and play a role in stabilizing in a complex pyrolysis environment.
(5) The active components such as ZSM-5, HZSM-5 and MCM-41 can be used independently, and metal compounds can be added in the preparation of the molecular sieve synthetic solution, so that metal ions are loaded on the surface, and the catalytic activity is improved; the specific surface area and the aperture of the molecular sieve are larger, the reactant can be better adsorbed on the catalyst, and meanwhile, the regular pore canal also has shape-selective catalysis effect, thereby being beneficial to improving the selectivity of product distribution; the metal compounds generally have more excellent redox properties, exhibit higher catalytic activity, and are highly and readily available. In summary, coFe compared to other oily sludge pyrolysis catalysts 2 O 4 @SiO 2 The catalytic capability of the catalyst material with the RC core-shell structure is strong, the yield of pyrolysis oil which is utilized once is more than 75%, the magnetic separation recovery rate reaches 95%, the activity of the magnetic thermocatalytic material which is recovered and regenerated twice is about 80% of that of the original catalytic material, the magnetic thermocatalytic material is difficult to deactivate and can be efficiently recovered, and the magnetic thermocatalytic material is an environment-friendly material which can be recycled and can be applied to the field of pyrolysis of oily sludge.
Drawings
FIG. 1 is a TEM image of the recyclable magnetic thermocatalytic material prepared in example 1;
FIG. 2 is a graph of pyrolysis oil yield and quality for examples 1-5 and comparative experiments 1-9;
FIG. 3 is a graph showing the recovery and regeneration effects of the catalysts of examples 1-5 and comparative experiments 1-9.
Detailed Description
Example 1
The preparation method of the recyclable magnetic thermocatalytic material comprises the following steps:
(1) Iron (III) acetylacetonate (Fe (acac)) in a molar ratio of 1:2 3 ) Cobalt (III) acetylacetonate (Co (acac) 3 ) And 0.269/g Octadecylamine (ODA) into 10/mL deionized water, stirring thoroughly for 2/h, placing into a high pressure reactor, reacting at 200deg.C for 24/h, cooling to room temperature, separating with ethanol (appropriate amount of ethanol is added into 50ml centrifuge tube) at 5000 rpmSeparating heart for 30min to obtain CoFe 2 O 4 Separating the solution, drying at 110deg.C for 48 and h, grinding to powder, and sieving with 30 mesh sieve to obtain CoFe 2 O 4 And (5) a crystal.
(2) CoFe of 0.1. 0.1 g 2 O 4 Crystals and sodium 1g dodecylbenzenesulfonate (C) 18 H 29 NaO 3 S, SDBS) was dispersed in deionized water of 20ml, 80ml ethanol was added to the mixture and after ultrasonic treatment at 100 Hz for 1h, 5ml ammonium hydroxide (25% by mass aqueous solution) and 800. Mu.l Tetraethoxysilane (TEOS) were added with continuous stirring at room temperature, the suspension was thoroughly stirred for 10 h, washed with deionized water, and dried at 80℃for 6h to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
(3) 2g CoFe is added into 20ml active component synthetic liquid 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 Mixed solution @ RC.
The active component synthetic liquid comprises the following components: ZSM-5, HZSM-5, MCM-41, metal oxide (e.g. CaO, mgO, fe) 2 O 3 ) And metal salt compounds (e.g. KOH, znCl 2 、K 2 CO 3 ) Etc.
The active ingredient composition in this example is defined as a ZSM-5 composition. The preparation method of the ZSM-5 synthetic solution comprises the following steps: solution a was prepared with 6g TEOS (tetraethoxysilane), 6.25g TPAOH (tetrapropylammonium hydroxide) and 50g deionized water; with 0.12g of Al (NO) 3 ) 3 ·9H 2 O, 0.25g NaOH and 2g deionized water to prepare solution B; then the solution A is heated and hydrolyzed by a water bath method at 35 ℃ for 24 h, and the solution B is added into the solution A under the condition of stirring to form a mixture with the molar ratio of n (Na 2 O)：n(Al 2 O 3 )：n(SiO 2 )：n(TPAOH)：n(H 2 O) =0.05: 0.0125:1:0.25: 60. Wherein Na is 2 O and Al 2 O 3 Is the product formed during the reaction. The purpose of TEOS is to provide a silicon source.
(4) CoFe is to be CoFe 2 O 4 @SiO 2 Transferring the @ RC mixed solution into a stainless steel crystallization kettle, placing the stainless steel crystallization kettle in an oven for crystallization at 160 ℃ for 48 h, cooling to room temperature, repeatedly flushing the material to neutrality with deionized water, drying 6h in the oven at 110 ℃, placing the material in a muffle furnace, and roasting 4h at 550 ℃ to burn out impurities to obtain the recyclable magnetic thermocatalytic material, namely CSZ-C 160 H 48 Core-shell structured catalytic material, CSZ-C 160 H 48 A TEM image of the core-shell structured catalytic material is shown in fig. 1.
The prepared recyclable magnetic thermocatalytic material, namely CSZ-C 160 H 48 The core-shell structure catalytic material is used in the catalytic pyrolysis of the oily sludge.
The recyclable magnetic thermocatalytic material is added in the following manner: 20 g of CSZ-C are taken 160 H 48 The core-shell structure catalytic material and 100 g oily sludge are uniformly mixed, the heat preservation is carried out on the mixture at 600 ℃ in a tube furnace for 1h (the heating rate of the tube furnace is 5 ℃/min), the yield of pyrolysis oil is measured, the reacted mixture is spread on sample paper after cooling, and the magnetic thermocatalytic material is sucked by a magnet to be separated from pyrolysis residues, so that the recovery rate of the magnetic thermocatalytic material is measured. And burning the recovered magnetic thermocatalytic material for 90 min at 500 ℃ in the atmosphere of 150 mL/min oxygen flow to obtain the regenerated magnetic thermocatalytic material. And (5) continuing the pyrolysis of the regenerated magnetic thermocatalytic material in the steps, and measuring the pyrolysis oil yield.
Example 2
The preparation method of the recyclable magnetic thermocatalytic material comprises the following steps:
(1) Iron (III) acetylacetonate (Fe (acac)) in a molar ratio of 1:2 3 ) Cobalt (III) acetylacetonate (Co (acac) 3 ) Dissolving 0.269/g Octadecylamine (ODA) in 10 mL deionized water, stirring thoroughly for 2h, placing into a high pressure reaction kettle, reacting at 200deg.C for 24 h, cooling to room temperature, centrifuging with ethanol (added into 50ml centrifuge tube) at 5000 rpm for 30min to obtain CoFe 2 O 4 Drying the separated solution at 110deg.C for 48 and h, grinding to obtain powder, sieving with 30 mesh sieve to obtain CoFe 2 O 4 And (5) a crystal.
(2) CoFe of 0.1. 0.1 g 2 O 4 Crystals and sodium 1g dodecylbenzenesulfonate (C) 18 H 29 NaO 3 S, SDBS) was dispersed in deionized water of 20ml, 80ml ethanol was added to the mixture and after ultrasonic treatment at 100 Hz for 1h, 5ml ammonium hydroxide (25% by mass aqueous solution) and 800. Mu.l Tetraethoxysilane (TEOS) were added with continuous stirring at room temperature, the suspension was thoroughly stirred for 10 h, washed with deionized water, and dried at 80℃for 6h to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
(3) 2g CoFe is added into 20ml active component synthetic liquid 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 Mixed solution @ RC.
The active component synthetic liquid comprises the following components: ZSM-5 synthesis solution, HZSM-5 synthesis solution, MCM-41 synthesis solution, and metal oxide (such as CaO, mgO, fe) 2 O 3 ) And metal salt compounds (e.g. KOH, znCl 2 、K 2 CO 3 ) Etc.
The active ingredient synthesis liquid is defined as HZSM-5 synthesis liquid in the embodiment. The preparation method of the HZSM-5 synthetic solution comprises the following steps: 14.2g TPABr is dissolved in 80g deionized water and stirred for 1. 1h, 84.12 g NH is added 3 ·H 2 O (25% by mass) was stirred for 0.5. 0.5 h, and 4 g of Al (NO) was added 3 ) 3 ·9H 2 O and 80g TEOS were stirred 1h to form a molar ratio n (SiO 2 )：n(Al 2 O 3 )：n(TPABr)：n(NH 3 ·9H 2 O)：n(H 2 O) =100: 1:10:150:1100 HZSM-5 synthesis solution.
(4) CoFe is to be CoFe 2 O 4 @SiO 2 Transferring the @ RC mixed solution into a stainless steel crystallization kettle, placing the stainless steel crystallization kettle in a baking oven for crystallization at 160 ℃ for 48 h, cooling to room temperature, repeatedly washing the material to neutrality with deionized water, drying 6h in the baking oven at 110 ℃, placing the material in a muffle furnace, baking 4h at 550 ℃ for impurity burning to obtain CSHZ-C 160 H 48 The core-shell structure can recycle the magnetic thermocatalytic material.
The prepared CSHZ-C 160 H 48 Core-shellThe magnetic thermocatalytic material with recoverable structure is used in catalytic pyrolysis of oily sludge.
The adding mode is as follows: 20 g of CSHZ-C is taken 160 H 48 The recoverable magnetic thermocatalytic material with the core-shell structure and 100 g oily sludge are uniformly mixed, the heat preservation is carried out on the mixture at the temperature of 600 ℃ in a tube furnace for 1h (the heating rate of the tube furnace is 5 ℃/min), the yield of pyrolysis oil is measured, the mixture after cooling is spread on sample paper, the recoverable magnetic thermocatalytic material is absorbed by a magnet, the recoverable magnetic thermocatalytic material is separated from pyrolysis residues, and the recovery rate of the recoverable magnetic thermocatalytic material is measured. And burning the recovered recoverable magnetic thermocatalytic material for 90 minutes at 500 ℃ in the atmosphere of 150 mL/min oxygen flow to obtain the regenerated magnetic thermocatalytic material. And (5) continuing the pyrolysis of the regenerated magnetic thermocatalytic material in the steps, and measuring the pyrolysis oil yield.
Example 3
The preparation method of the recyclable magnetic thermocatalytic material comprises the following steps:
(1) Iron (III) acetylacetonate (Fe (acac)) in a molar ratio of 1:2 3 ) Cobalt (III) acetylacetonate (Co (acac) 3 ) Dissolving 0.269/g Octadecylamine (ODA) in 10 mL deionized water, stirring thoroughly for 2h, placing into a high pressure reaction kettle, reacting at 200deg.C for 24 h, cooling to room temperature, centrifuging with ethanol (added into 50ml centrifuge tube) at 5000 rpm for 30min to obtain CoFe 2 O 4 Drying the separated solution at 110deg.C for 48 and h, grinding to obtain powder, sieving with 30 mesh sieve to obtain CoFe 2 O 4 And (5) a crystal.
(2) CoFe of 0.1. 0.1 g 2 O 4 Crystals and sodium 1g dodecylbenzenesulfonate (C) 18 H 29 NaO 3 S, SDBS) was dispersed in deionized water of 20ml, 80ml ethanol was added to the mixture and after ultrasonic treatment at 100 Hz for 1h, 5ml ammonium hydroxide (25% by mass aqueous solution) and 800. Mu.l Tetraethoxysilane (TEOS) were added with continuous stirring at room temperature, the suspension was thoroughly stirred for 10 h, washed with deionized water, and dried at 80℃for 6h to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
(3) 2g CoFe is added into 20ml active component synthetic liquid 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 Mixed solution @ RC.
The active component synthetic liquid comprises the following components: ZSM-5 synthesis solution, HZSM-5 synthesis solution, MCM-41 synthesis solution, and metal oxide (such as CaO, mgO, fe) 2 O 3 ) And metal salt compounds (e.g. KOH, znCl 2 、K 2 CO 3 ) Etc.
The active ingredient composition liquid is defined as MCM-41 composition liquid in the embodiment. The preparation method of the MCM-41 synthetic solution comprises the following steps: 144.3 g of NaOH and 43.5. 43.5 g silica sol (containing 40 mass percent of SiO 2) are stirred at 75 ℃ for 1h by taking CTAB (cetyltrimethylammonium bromide) as a template agent, 96.0. 96.0 g of CTAB and 298.0 g of deionized water are added for stirring for 1h, and the molar ratio of n (SiO 2 is finally formed 2 )：n(Na 2 O)：n(CTAB)：n(H 2 O) =1: 0.25:0.25:100 MCM-41 synthesis solution.
(4) CoFe is to be CoFe 2 O 4 @SiO 2 Transferring the @ RC mixed solution into a stainless steel crystallization kettle, placing the stainless steel crystallization kettle in an oven for crystallization at 180 ℃ for 24 h, cooling to room temperature, repeatedly washing the material to neutrality with deionized water, drying 6h in the oven at 110 ℃, placing the material in a muffle furnace, and roasting 4h at 550 ℃ to burn out impurities to obtain CSM-C 160 H 48 The core-shell structure catalytic material is the recyclable magnetic thermocatalytic material.
Prepared CSM-C 160 H 48 The core-shell structure catalytic material is used in the catalytic pyrolysis of the oily sludge.
The adding mode is as follows: 20 g of CSM-C was taken 160 H 48 The core-shell structure catalytic material and 100 g oily sludge are uniformly mixed, the mixture is subjected to pyrolysis at 600 ℃ in a tube furnace at a temperature-keeping speed of 1h (the heating rate of the tube furnace is 5 ℃/min), the yield of pyrolysis oil is measured, the cooled mixture is spread on sample paper, the magnetic thermal catalytic material is sucked by a magnet, the magnetic thermal catalytic material is separated from pyrolysis residues, and the recovery rate of the magnetic thermal catalytic material is measured. The recovered magnetic thermocatalytic material is subjected to 500 ℃ in the atmosphere of oxygen flow of 150 mL/minBurning for 90 min to obtain regenerated magnetic thermocatalytic material. And (5) continuing the pyrolysis of the regenerated magnetic thermocatalytic material in the steps, and measuring the pyrolysis oil yield.
Example 4
The preparation method of the recyclable magnetic thermocatalytic material comprises the following steps:
(1) Iron (III) acetylacetonate (Fe (acac)) in a molar ratio of 1:2 3 ) Cobalt (III) acetylacetonate (Co (acac) 3 ) Dissolving 0.269-g Octadecylamine (ODA) in 10 mL deionized water, stirring thoroughly for 2h, placing into a high-pressure reaction kettle, reacting at 200deg.C for 24 h, cooling to room temperature, centrifuging with ethanol (added into 50ml centrifuge tube at proper amount of ethanol) at 5000 rpm for 30min to obtain CoFe 2 O 4 Drying the separated solution at 110deg.C for 48 and h, grinding to obtain powder, sieving with 30 mesh sieve to obtain CoFe 2 O 4 And (5) a crystal.
(2) CoFe of 0.1. 0.1 g 2 O 4 Crystals and 1g sodium dodecylbenzenesulfonate (C) 18 H 29 NaO 3 S, SDBS) was dispersed in deionized water of 20ml, 80ml ethanol was added to the mixture and after ultrasonic treatment at 100 Hz for 1h, 5ml ammonium hydroxide (25% by mass aqueous solution) and 800. Mu.l Tetraethoxysilane (TEOS) were added with continuous stirring at room temperature, the suspension was thoroughly stirred for 10 h, washed with deionized water, and dried at 80℃for 6h to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
(3) To 20ml ZSM-5 active component synthesis solution was added 2g of CoFe 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 Mixed solution @ RC.
The preparation method of ZSM-5 active component synthetic solution comprises the following steps: solution A was prepared with 6g TEOS (tetraethoxysilane), 6.25g TPAOH (tetrapropylammonium hydroxide) and 50g deionized water, and with 0.12g Al (NO) 3 ) 3 ·9H 2 O, 0.25g NaOH and 2g deionized water to prepare solution B; then the solution A is heated and hydrolyzed by a water bath method at 35 ℃ for 24 h, and the solution B is added into the solution A under stirring to form molesThe molar ratio is n (Na 2 O)：n(Al 2 O 3 )：n(SiO 2 )：n(TPAOH)：n(H 2 O) =0.05: 0.0125:1:0.25: 60.
(4) CoFe is to be CoFe 2 O 4 @SiO 2 Transferring the @ RC mixed solution into a stainless steel crystallization kettle, placing the stainless steel crystallization kettle in a baking oven for crystallization at 140 ℃ for 24 h, cooling to room temperature, repeatedly washing the material to neutrality with deionized water, drying the material in the baking oven at 110 ℃ for 6h, placing the material in a muffle furnace, baking the material at 550 ℃ for 4h, and burning out impurities to obtain CSZ-C 140 H 24 The core-shell structure catalytic material is the recyclable magnetic thermocatalytic material.
Prepared CSZ-C 140 H 24 The core-shell structure catalytic material is used in the catalytic pyrolysis of the oily sludge.
The adding mode is as follows: 20 g of CSZ-C are taken 140 H 24 The core-shell structure catalytic material and 100 g oily sludge are uniformly mixed, the mixture is subjected to pyrolysis at 600 ℃ in a tube furnace at a temperature of 1h (the heating rate is 5 ℃/min), the yield of pyrolysis oil is measured, the cooled mixture after the reaction is spread on sample paper, the magnetic thermocatalytic material is sucked by a magnet, the magnetic thermocatalytic material is separated from pyrolysis residues, and the recovery rate of the magnetic thermocatalytic material is measured. And burning the recovered magnetic thermocatalytic material for 90 min at 500 ℃ in the atmosphere of 150 mL/min oxygen flow to obtain the regenerated magnetic thermocatalytic material. And (5) continuing the pyrolysis of the regenerated magnetic thermocatalytic material in the steps, and measuring the pyrolysis oil yield.
Example 5
The preparation method of the recyclable magnetic thermocatalytic material comprises the following steps:
(1) Iron (III) acetylacetonate (Fe (acac)) in a molar ratio of 1:2 3 ) Cobalt (III) acetylacetonate (Co (acac) 3 ) Dissolving 0.269/g Octadecylamine (ODA) in 10 mL deionized water, stirring thoroughly for 2h, placing into a high pressure reaction kettle, reacting at 200deg.C for 24 h, cooling to room temperature, centrifuging with ethanol (added into 50ml centrifuge tube) at 5000 rpm for 30min to obtain CoFe 2 O 4 Drying the separated solution at 110deg.C for 48 and h, grinding to obtain powder, sieving with 30 mesh sieve to obtainCoFe 2 O 4 And (5) a crystal.
(2) CoFe of 0.1. 0.1 g 2 O 4 Crystals and sodium 1g dodecylbenzenesulfonate (C) 18 H 29 NaO 3 S, SDBS) was dispersed in deionized water of 20ml, 80ml ethanol was added to the mixture and after ultrasonic treatment at 100 Hz for 1h, 5ml ammonium hydroxide (25% by mass aqueous solution) and 800. Mu.l Tetraethoxysilane (TEOS) were added with continuous stirring at room temperature, the suspension was thoroughly stirred for 10 h, washed with deionized water, and dried at 80℃for 6h to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
(3) To 20ml ZSM-5 active component synthesis solution was added 2g of CoFe 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 Mixed solution @ RC.
The preparation method of the ZSM-5 active component synthetic solution comprises the following steps: solution a was prepared with 6g teos (tetraethoxysilane), 6.25g tpaoh (tetrapropylammonium hydroxide) and 50g deionized water; with 0.12g Al (NO) 3 ) 3 ·9H 2 O, 0.25g NaOH and 2g deionized water to prepare solution B; then the solution A is heated and hydrolyzed by a water bath method at 35 ℃ for 24 h, and the solution B is added into the solution A under the condition of stirring to form a mixture with the molar ratio of n (Na 2 O)：n(Al 2 O 3 )：n(SiO 2 )：n(TPAOH)：n(H 2 O) =0.05: 0.0125:1:0.25:60, and a ZSM-5 active component synthesis solution.
(4) CoFe is to be CoFe 2 O 4 @SiO 2 Transferring the @ RC mixed solution into a stainless steel crystallization kettle, placing the stainless steel crystallization kettle in a drying oven for crystallization at 160 ℃ for 72 h, cooling to room temperature, repeatedly washing the material to neutrality with deionized water, drying 6h in the drying oven at 110 ℃, placing the material in a muffle furnace, and roasting 4h at 550 ℃ to burn out impurities to obtain CSZ-C 180 H 72 The core-shell structure catalytic material (namely the recyclable magnetic thermocatalytic material) is prepared.
Prepared CSZ-C 180 H 72 The core-shell structure catalytic material is used in the catalytic pyrolysis of the oily sludge.
The adding mode is as follows: 20 g of CSZ-C are taken 180 H 72 The core-shell structure catalytic material and 100 g oily sludge are uniformly mixed, the mixture is subjected to pyrolysis at 600 ℃ in a tube furnace at a temperature-keeping speed of 1h (the heating rate of the tube furnace is 5 ℃/min), the yield of pyrolysis oil is measured, the cooled mixture is spread on sample paper, the magnetic thermal catalytic material is sucked by a magnet, the magnetic thermal catalytic material is separated from pyrolysis residues, and the recovery rate of the magnetic thermal catalytic material is measured. And burning the recovered magnetic thermocatalytic material for 90 min at 500 ℃ in the atmosphere of 150 mL/min oxygen flow to obtain the regenerated magnetic thermocatalytic material. And (5) continuing the pyrolysis of the regenerated magnetic thermocatalytic material in the steps, and measuring the pyrolysis oil yield.
Comparative experiment 1
A method for preparing a recyclable magnetic thermocatalytic material is similar to example 1, except that in step (1), iron acetylacetonate, cobalt acetylacetonate and 0.2g of octadecylamine are dissolved in a molar ratio of 1:1.
Comparative experiment 2
A method for preparing a recyclable magnetic thermocatalytic material is similar to example 1, except that in step (1), iron acetylacetonate, cobalt acetylacetonate and 0.3g of octadecylamine are dissolved in a molar ratio of 1:3.
Comparative experiment 3
A method for preparing recoverable magnetic thermocatalytic material is similar to example 1, except that in step (1), ferric acetylacetonate, cobalt acetylacetonate and octadecylamine are dissolved, then put into a high-pressure reaction kettle to react at 180 ℃ for 12h, cooled and repeatedly centrifuged at 5000 rpm with ethanol to obtain CoFe 2 O 4 The separated solution was dried 48 h at 100 ℃ and ground to a powder.
Comparative experiment 4
A method for preparing recoverable magnetic thermocatalytic material is similar to example 1, except that in step (1), ferric acetylacetonate, cobalt acetylacetonate and octadecylamine are dissolved, then put into a high-pressure reaction kettle to react at 220 ℃ for 36h, cooled and repeatedly centrifuged at 5000 rpm with ethanol to obtain CoFe 2 O 4 Drying the separated solution at 120deg.C for 48 and h, and grinding to obtain a powderAnd (3) powder.
Comparative experiment 5
A method for preparing a recyclable magnetic thermocatalytic material, similar to example 1, except that in step (2), ammonium hydroxide is 10% by mass in aqueous solution.
Comparative experiment 6
A method for preparing a recyclable magnetic thermocatalytic material, similar to example 1, except that in step (2), ammonium hydroxide is 40% aqueous by mass.
Comparative experiment 7
A method for preparing a recyclable magnetic thermocatalytic material, similar to example 1, except that in step (3), 1g of CoFe prepared in step (2) is added to 15ml of the active ingredient composition 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 @ RC mixed solution.
Comparative experiment 8
A method for preparing a recyclable magnetic thermocatalytic material is similar to example 1, except that in step (3), 3g CoFe prepared in step (2) is added to a 25ml active ingredient composition 2 O 4 @SiO 2 Core-shell structure particles, pH is regulated to be neutral, and CoFe is formed 2 O 4 @SiO 2 @ RC mixed solution.
Comparative experiment 9
A method for preparing a recyclable magnetic thermocatalytic material is similar to that of example 1, except that in the step (3), the active component synthesis liquid is ZSM-5 synthesis liquid and a metal compound ZnCl 2 To 30ml of ZSM-5 synthesis solution was added ZnCl with a mass fraction of 20% of 6ml 2 The solution is such that the mass ratio of Zn to ZSM-5 is 1:50, impregnating 12h under stirring. FIG. 2 is a graph of pyrolysis oil yield and quality for examples 1-5 and comparative experiments 1-9; FIG. 3 is a graph showing the recovery and regeneration effects of the catalysts of examples 1-5 and comparative experiments 1-9.
The present application is not limited to the above-mentioned embodiments, and any person skilled in the art, based on the technical solution of the present application and the inventive concept thereof, can be replaced or changed within the scope of the present application.

Claims (10)

1. A recyclable magnetic thermocatalytic material, characterized by: the recoverable magnetic thermocatalytic material is CoFe 2 O 4 @SiO 2 Catalytic material with @ RC core-shell structure and CoFe 2 O 4 Is a shell with a core-shell structure, siO 2 The active component is a catalytic layer.
2. A method of preparing a recyclable magnetic thermocatalytic material as claimed in claim 1, wherein: the method comprises the following steps:
(1) Preparation of CoFe by hydrothermal method 2 O 4 A crystal;
(2) The CoFe obtained in the step (1) is treated 2 O 4 The crystal adopts St method to load SiO 2 Preparation of CoFe 2 O 4 @SiO 2 Core-shell structured particles;
(3) The CoFe obtained in the step (2) is treated 2 O 4 @SiO 2 The core-shell structure particles are immersed into the active component synthesis liquid to form CoFe 2 O 4 @SiO 2 An @ RC mixed solution;
(4) The CoFe obtained in the step (3) is treated 2 O 4 @SiO 2 Crystallizing the @ RC mixed solution to obtain CoFe 2 O 4 @SiO 2 The @ RC may recover the magnetic thermocatalytic material.
3. The method for preparing the recyclable magnetic thermocatalytic material as claimed in claim 2, wherein: in step (1), coFe is prepared 2 O 4 When in crystallization, ferric acetylacetonate and cobalt acetylacetonate are taken as materials, ferric acetylacetonate, cobalt acetylacetonate and 0.2g-0.3g octadecylamine with the molar ratio of 1:1-3 are dissolved and then put into a high-pressure reaction kettle to react, the temperature is reduced after the reaction, and the CoFe is obtained by repeated centrifugation 2 O 4 Separating the solution and separating CoFe 2 O 4 Drying the separated solution and grinding the dried solution to powder to obtain CoFe 2 O 4 And (5) a crystal.
4. A method for preparing a recyclable magnetic thermocatalytic material as claimed in claim 3, wherein: firstly, ferric acetylacetonate, cobalt acetylacetonate and octadecylamine are dissolved and then put into a high-pressure reaction kettle to react at 180-220 ℃ for 12-36 h, ethanol is used for repeated centrifugal separation at 5000 rpm after the temperature is reduced, and the obtained CoFe is obtained 2 O 4 Drying the separated solution at 100-120deg.C for 48 h, and grinding to obtain CoFe powder 2 O 4 And (5) a crystal.
5. The method for preparing the recyclable magnetic thermocatalytic material as claimed in claim 2, wherein: in step (2), coFe is prepared 2 O 4 @SiO 2 The core-shell structure particles comprise the following specific steps: the CoFe obtained in the step (1) is treated 2 O 4 Dispersing the crystal and sodium dodecyl benzene sulfonate into deionized water, performing ultrasonic treatment, adding ammonium hydroxide and tetraethoxysilane, stirring, washing and drying to obtain CoFe 2 O 4 @SiO 2 Core-shell structured particles.
6. The method for preparing the recyclable magnetic thermocatalytic material as claimed in claim 2, wherein: in the step (3), the CoFe prepared in the step (2) of 1 to 3g is added 2 O 4 @SiO 2 Adding the core-shell structure particles into 15-25 ml active component synthetic liquid, regulating pH to neutrality, and forming CoFe 2 O 4 @SiO 2 Mixed solution @ RC.
7. The method for preparing the recyclable magnetic thermocatalytic material as claimed in claim 6, wherein: in the step (3), the active component synthesis liquid comprises any one or more of ZSM-5 synthesis liquid, HZSM-5 synthesis liquid, MCM-41 synthesis liquid, metal oxide and metal salt compound.
8. The method for preparing the recyclable magnetic thermocatalytic material as claimed in claim 2, wherein: in the step (4), coFe prepared in the step (3) is used 2 O 4 @SiO 2 The crystallization treatment method of the @ RC mixed solution comprises the following steps: coFe is to be CoFe 2 O 4 @SiO 2 Crystallizing the @ RC mixed solution in an oven, cooling, washing to neutrality, drying, and calcining to obtain CoFe 2 O 4 @SiO 2 The @ RC may recover the magnetic thermocatalytic material.
9. The method for preparing the recyclable magnetic thermocatalytic material as claimed in claim 8, wherein: coFe 2 O 4 @SiO 2 When the mixed solution @ RC is crystallized in an oven, the temperature is set to be 130-190 ℃ and the reaction time is 24 h-72 h.
10. Use of a recyclable magnetic thermocatalytic material obtained by the preparation process according to any of claims 2-9 for pyrolysis of oily sludge, increasing yield and quality of pyrolysis oil.
CN202310413793.9A 2023-04-18 2023-04-18 Recyclable magnetic thermocatalytic material and preparation method and application thereof Pending CN116713031A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310413793.9A CN116713031A (en) 2023-04-18 2023-04-18 Recyclable magnetic thermocatalytic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310413793.9A CN116713031A (en) 2023-04-18 2023-04-18 Recyclable magnetic thermocatalytic material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116713031A true CN116713031A (en) 2023-09-08

Family

ID=87863817

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310413793.9A Pending CN116713031A (en) 2023-04-18 2023-04-18 Recyclable magnetic thermocatalytic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116713031A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101299366A (en) * 2008-03-13 2008-11-05 复旦大学 Magnetic inorganic nano corpuscle/zeolite nucleocapsid type composite microsphere and preparation method thereof
CN107335403A (en) * 2017-06-29 2017-11-10 上海工程技术大学 Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle
CN108101114A (en) * 2017-12-21 2018-06-01 湖南大学 A kind of nanometer ferrite composite material of bivalve layer structure and preparation method thereof
CN110697791A (en) * 2019-11-15 2020-01-17 林卿 Core-shell structure Fe3O4Preparation method of @ Beta magnetic nano composite material
CN113371726A (en) * 2021-06-25 2021-09-10 复旦大学 Functional zeolite molecular sieve material and preparation method thereof
CN113441172A (en) * 2021-06-25 2021-09-28 西安科技大学 Magnetic core-shell structure catalyst and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101299366A (en) * 2008-03-13 2008-11-05 复旦大学 Magnetic inorganic nano corpuscle/zeolite nucleocapsid type composite microsphere and preparation method thereof
CN107335403A (en) * 2017-06-29 2017-11-10 上海工程技术大学 Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle
CN108101114A (en) * 2017-12-21 2018-06-01 湖南大学 A kind of nanometer ferrite composite material of bivalve layer structure and preparation method thereof
CN110697791A (en) * 2019-11-15 2020-01-17 林卿 Core-shell structure Fe3O4Preparation method of @ Beta magnetic nano composite material
CN113371726A (en) * 2021-06-25 2021-09-10 复旦大学 Functional zeolite molecular sieve material and preparation method thereof
CN113441172A (en) * 2021-06-25 2021-09-28 西安科技大学 Magnetic core-shell structure catalyst and preparation method thereof

Similar Documents

Publication Publication Date Title
CN106732509B (en) Preparation method, catalytic ozone oxidation catalyst and its application of modified aluminium oxide supports
CN101948140B (en) Method for preparing Fe2O3 and Fe3O4 nano materials by taking F2<2+> salt as raw material
CN107522389B (en) Micro-nano bioactive glass microsphere with surface nano-pore structure and preparation method thereof
CN110124729B (en) Coated catalyst for slurry bed Fischer-Tropsch synthesis and preparation method thereof
CN111992232B (en) Supported transition metal carbide and preparation method and application thereof
CN110124711B (en) Preparation method and desulfurization application of few-layer carbon nitride loaded tungsten trioxide nanoparticle catalyst
CN111330648A (en) MIL-101(Fe)/g-C3N4Composite visible light photocatalyst and preparation method and application thereof
CN113371726A (en) Functional zeolite molecular sieve material and preparation method thereof
CN111905777A (en) Perovskite type lead cesium bromide quantum dot composite Bi2WO6Photocatalyst and preparation method thereof
CN112246283A (en) Bismuth tungstate @ MIL-100(Fe) composite material and preparation method and application thereof
CN108927138B (en) Bi2O3/diatomite composite photocatalytic material and preparation method thereof
CN113120977B (en) Method for preparing nickel ferrite nano material from nickel-containing ferroelectric plating wastewater and application thereof
CN110624507A (en) Preparation method and adsorption performance of 4A molecular sieve composite material
CN116713031A (en) Recyclable magnetic thermocatalytic material and preparation method and application thereof
CN102826568B (en) The preparation method of nanocrystalline ZSM-5 zeolite cluster and nanocrystalline ZSM-5 zeolite cluster obtained by this method
CN111135839B (en) Iron oxide modified attapulgite/bismuth molybdate composite photocatalyst and preparation method and application thereof
CN101239325B (en) Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof
CN108187609A (en) A kind of sepiolite supported nano zeroth order iron material and its preparation process and purposes
CN115501897B (en) Nanocomposite, preparation method and application thereof in hydrogen production by visible light catalysis
CN112675857B (en) Catalyst for improving naphthene content in tar by low-rank coal microwave pyrolysis and preparation method and application thereof
CN114345391A (en) Carbon nitride/graphene/manganese dioxide bifunctional catalyst and preparation method and application thereof
CN111468182B (en) Synthesis method of hollow titanium-silicon molecular sieve TS-1
CN113856680A (en) Magnetic carbon-doped spinel copper ferrite catalyst and preparation method and application thereof
US8642500B2 (en) Method for manufacturing iron catalyst
CN116003821B (en) MOF nano material and preparation method thereof, preparation method and application of metal-loaded single-atom MOF nano material

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