CN114522699B - Method for removing oil on surface of waste oil refining catalyst - Google Patents

Method for removing oil on surface of waste oil refining catalyst Download PDF

Info

Publication number
CN114522699B
CN114522699B CN202210207554.3A CN202210207554A CN114522699B CN 114522699 B CN114522699 B CN 114522699B CN 202210207554 A CN202210207554 A CN 202210207554A CN 114522699 B CN114522699 B CN 114522699B
Authority
CN
China
Prior art keywords
catalyst
oil
hydrogen peroxide
oil refining
waste oil
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
CN202210207554.3A
Other languages
Chinese (zh)
Other versions
CN114522699A (en
Inventor
吕岳奋
张广积
沈蔡龙
李媛媛
杨超
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.)
Yabang Green Process And New Materials Research Institute Nanjing Co ltd
Institute of Process Engineering of CAS
Nanjing Tech University
Original Assignee
Yabang Green Process And New Materials Research Institute Nanjing Co ltd
Institute of Process Engineering of CAS
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 Yabang Green Process And New Materials Research Institute Nanjing Co ltd, Institute of Process Engineering of CAS, Nanjing Tech University filed Critical Yabang Green Process And New Materials Research Institute Nanjing Co ltd
Priority to CN202210207554.3A priority Critical patent/CN114522699B/en
Publication of CN114522699A publication Critical patent/CN114522699A/en
Application granted granted Critical
Publication of CN114522699B publication Critical patent/CN114522699B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/70—Wet oxidation of material submerged in liquid
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention provides a method for removing oil on the surface of a waste oil refining catalyst, which comprises the following steps: mixing the ground waste oil refining catalyst with a hydrogen peroxide solution with the concentration of 5-15 wt% or a persulfate solution with the concentration of 50-100 mmol/L, and carrying out solid-liquid separation after reaction to obtain a deoiled catalyst; the method utilizes metal ions in the waste oil refining catalyst to catalyze hydrogen peroxide or persulfate to generate Fenton-like effect, so that the oil quality on the surface of the waste oil refining catalyst is removed, the method can thoroughly oxidize and decompose oil substances, the oil quality removal is realized in a green and environment-friendly way, the whole treatment process is simple to operate, and the requirement on equipment is low; in addition, hydrogen peroxide or persulfate is used as a reactant, so that other impurities are not introduced to pollute a sample, and the problem of environmental pollution caused by harmful gas generated in the oil removal process or the use of an organic solvent is avoided, thereby being beneficial to industrial application.

Description

Method for removing oil on surface of waste oil refining catalyst
Technical Field
The invention belongs to the technical field of recycling of waste catalysts, and particularly relates to a method for removing oil on the surface of a waste oil refining catalyst.
Background
In recent years, the total amount of waste oil refining catalysts produced by the petroleum refining industry in China rises year by year, wherein only about one tenth of the waste oil refining catalysts are recycled, and the rest of the waste oil refining catalysts can only be processed in a piling mode. The waste oil refining catalyst belongs to dangerous waste, contains a large amount of heavy metals, and has high environmental risk of long-term storage. In the form of Ni, mo/Al 2 O 3 Hydrogenation catalysts are exemplified, such catalysts are generally gamma-Al 2 O 3 Is a carrier, and Ni and Mo are main active components. Because of the metal V, ni in petroleum and the deposition of coke, the catalyst also contains a large amount of metal V after being scrapped, so the scrapped oil refining hydrogenation catalyst can be applied to the recovery of valuable metals such as V, ni. Since the oil refining catalyst is in contact with petroleum for a long time, a certain amount of oil exists on the surface of the oil refining catalyst. Because the oil coating on the surface of the spent catalyst can prevent the chemical reaction, the prior process for recovering metals from the spent catalyst requires deoiling pretreatment of the spent catalyst before heavy metals are extracted.
At present, the deoiling pretreatment of the waste oil refining catalyst mainly comprises an ultrasonic-assisted ethanol cleaning method, a low-pressure deoiling method, a surfactant washing method, a roasting method, an n-heptane extraction method, a toluene Soxhlet extraction method and the like. The ultrasonic-assisted ethanol cleaning method utilizes cavitation of ultrasonic waves to assist the environment-friendly polar solvent ethanol to extract and remove the oil on the surface of the spent catalyst. The low pressure deoiling process is to control certain temperature and to eliminate volatile oil and less cleavable matter from waste catalyst via distillation and condensation. The surfactant washing method uses the emulsification of surfactant to peel oil from the surface of waste oil refining catalyst, so as to attain the goal of deoiling waste catalyst. The roasting method is to oxidize and remove the oil on the surface of the waste catalyst at high temperature, and the high-temperature roasting degreasing method is simple to operate and has low requirements on equipment, but the whole process has huge energy consumption, waste gas and dust can be generated at the same time, and a quite complex post-treatment process is needed to avoid polluting the environment. The Soxhlet extraction method utilizes the property that oil can be dissolved in organic solvent, adds organic solvent such as n-heptane or toluene into a Soxhlet extractor to repeatedly extract the waste catalyst, and finally removes the oil on the surface of the waste catalyst. The Soxhlet extraction method requires longer time, and a large amount of organic solvents are used, so that the method does not meet the national green and environment-friendly requirements.
Chinese journal paper Dong Wei waste catalyst degreasing experiment research [ J ]. Petrochemical technology, 2021,28 (05) ", chinese journal paper Cheng Gongwei waste catalyst degreasing experiment analysis [ J ]. Chinese equipment engineering, 2020 (15)", and Chinese doctor's institute paper Wang Lu, ultrasonic assisted oil refining waste catalyst degreasing experiment research [ D ]. Kunming university, 2018. "A method for ultrasonically assisted oil refining catalyst degreasing is provided, specifically, a domestic SKTC-500 ultrasonic device with a frequency of 20.21kHz is adopted, waste catalyst and ethanol are added into a three-necked flask, and then the three-necked flask is placed in a thermostat with a magnetic stirring function for ultrasonic degreasing. Finally, the conclusion is that the oil removal rate can reach 99.8% under the conditions that the temperature is 55 ℃, the ultrasonic time is 120min, the ultrasonic power is 600W and the solid-liquid ratio is 5:1. It is reported that this method can efficiently remove the oil on the surface of the spent catalyst, but it requires a large amount of ethanol, which is an organic solvent, and is liable to cause ethanol waste; more importantly, the requirements of the method for temperature and ultrasonic power limit the application of the method in large-scale reaction equipment.
Chinese journal papers "Liu Yong, chen Shaochun, liu Zhenzhen, liu Mudan. Low pressure deoiling pretreatment study of spent oil-containing petrochemical catalysts [ J]The Chinese resource comprehensive utilization, 2010,28 (11) "proposes a low-pressure deoiling method for removing the oil on the surface of the dead catalyst. Under the action of vacuum pump, a low-pressure environment is formed, then the oil quality and less part of cleavable substances on the surface of the waste catalyst are evaporated and removed by adopting a heating and condensing method, so as to achieve the aim of deoiling pretreatment of the waste catalyst, and after the subsequent condensing operationThe vaporized oil was recovered. The experimental conditions were continuously optimized to finally conclude that the pressure was 2×10 4 Under the condition of Pa, the temperature is raised at the speed of 9.0 ℃/min, the final temperature reaches 550 ℃, and the temperature is kept for 1h. The oil removal rate of the low-pressure deoiling method can reach 110.83 percent (more than 100 percent of main reasons are that non-oily organic matters are cracked to generate oil) compared with the organic solvent extraction method. The method needs high-temperature low-pressure conditions, has high requirements on a reaction device and has higher operation difficulty.
The method for removing the oil on the surface of the waste catalyst by using surfactant washing is proposed by the Chinese journal paper Zhang Yuna, zhang Qin, xin Changbo, yuzhen, liu and Wu Yue, the method for removing the oil on the surface of the waste hydrogenation catalyst is proposed by the university of Dalian university, J, university, 2008 (03), the author designs and synthesizes the surfactant which has excellent high-temperature stability, excellent chemical stability, strong electrolyte resistance and good water solubility, and finally the conclusion is obtained by continuously optimizing the experimental conditions, when the mass fraction of the self-made surfactant is 3%, the mass fraction of NaOH is 3%, the mass fraction of NaCl is 1%, the volume ratio of oil to water is 1:2, and the oil removal rate is 83.9% under the ultrasonic wave effect when the temperature is 80 ℃. CN105498860a discloses a deoiling method for oil-containing waste catalyst, and the technical scheme is characterized in that: crushing the waste catalyst to a particle size smaller than 1000 mu m, and controlling the deoiling conditions to be that the mass ratio of water to the waste catalyst is 12-6:1, the mass concentration of NaOH and surfactant is respectively controlled to be 0.05-3 wt%, and the deoiling temperature is 40-100 ℃ within the range of 0.01-0.3 wt%. After the color of the deoiling washing liquid has no obvious change, the oil-containing liquid is separated from the solid by adopting the existing solid-liquid separation means. In the operation process of the method, various reactants are required to be added, certain reaction temperature and ultrasonic stirring conditions are required, and the whole operation process is complex and difficult to be applied to large-scale reaction equipment.
In summary, the method for ensuring that no harmful gas is generated in the deoiling treatment process of the spent catalyst and avoiding the use of organic solvents has very important significance.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for removing the oil on the surface of a waste oil refining catalyst, which realizes the aims of no harmful gas and no organic solvent in the oil removing process by using Fenton-like effect generated by an oxidant and metal in the waste oil refining catalyst, is environment-friendly and efficient, and has good application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for removing oil on the surface of a waste oil refining catalyst, which comprises the following steps:
mixing the ground waste oil refining catalyst with a hydrogen peroxide solution or a persulfate solution, and performing solid-liquid separation after reaction to obtain a deoiled catalyst;
the concentration of the hydrogen peroxide solution is 5 to 15wt%, for example, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The concentration of the persulfate solution is 50 to 100mmol/L, for example, 50 mmol/55 mmol/60 mmol/65 mmol/70 mmol/75 mmol/80 mmol/85 mmol/90 mmol/95 mmol/100 mmol/or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
According to the method, the Fenton-like effect is generated by catalyzing hydrogen peroxide or persulfate by utilizing metal ions in the waste oil refining catalyst, so that the oil quality on the surface of the waste oil refining catalyst is removed, the oil quality can be thoroughly oxidized and decomposed, the oil quality removal is realized in a green environment-friendly way, the whole treatment process is simple to operate, and the equipment requirement is low; in addition, hydrogen peroxide or persulfate is used as a reactant, so that other impurities are not introduced to pollute a sample, and the problem of environmental pollution caused by harmful gas generated in the oil removal process or the use of an organic solvent is avoided, thereby being beneficial to industrial application.
More specifically, the spent refinery catalyst contains various metal elements, such as Mo, ni, V, al, fe, wherein Ni, mo are the main active components of the refinery catalyst, al 2 O 3 As a carrier; in the petroleum refining process, metal elements Ni, V, fe, etc. in petroleum are also deposited on the surface of the spent catalyst. While Fe (II) or Fe (III), iron-containing minerals and other transition metals, such as Co, cd, cu, ag, mn, ni, etc. can catalyze H 2 O 2 The reaction generates hydroxyl free radical (OH) with extremely strong oxidizing property, and can also catalyze persulfate to generate sulfate radical (SO) 4 - Using hydroxyl radicals (. OH) or sulfate radicals (SO) 4 - The oil quality on the surface of the waste oil refining catalyst can be removed by oxidation due to the strong oxidizing property. And the waste oil refining catalyst can generate a new surface after being ground and crushed, so that the waste oil refining catalyst is matched with H 2 O 2 Or the contact area of the persulfate solution is increased, which is beneficial to hydroxyl radical (OH) or sulfate radical (SO) 4 - And. The formation of).
In the present invention, the concentration of the hydrogen peroxide solution is controlled. If the concentration is too low, the oil removal reaction effect is poor, and the aim of high-efficiency oil removal cannot be achieved; if the concentration is too high, H is excessively increased 2 O 2 The system temperature can be quickly increased, so that the hydrogen peroxide is decomposed in an ineffective way, and the purpose of removing oil can not be achieved.
In the present invention, the concentration of the persulfate solution also needs to be controlled. If the concentration is too low, the oil removal reaction effect is poor, and the aim of high-efficiency oil removal cannot be achieved; if the concentration is too high, free radical quenching reaction is easy to occur among sulfate radicals in a high-concentration persulfate system, so that the oil removal efficiency is not increased along with the increase of the concentration of the persulfate after reaching a peak value, and the waste of raw materials is caused.
In the present invention, when the spent refinery catalyst is mixed with the hydrogen peroxide solution or the persulfate solution, it is preferable that the mixing order is such that the hydrogen peroxide solution or the persulfate solution is added to the vessel first and then the ground spent catalyst is added thereto.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, the spent refinery catalyst comprises one or a combination of at least two of a desulfurization hydrogenation catalyst, a catalytic cracking catalyst or a catalytic reforming catalyst, and the combination is typically, but not limited to, as exemplified by: a combination of a desulfurization hydrogenation catalyst and a catalytic cracking catalyst, a combination of a catalytic cracking catalyst and a catalytic reforming catalyst, a combination of a desulfurization hydrogenation catalyst, a catalytic cracking catalyst and a catalytic reforming catalyst, and the like.
As a preferred embodiment of the present invention, the grinding is performed using an agate mortar.
Preferably, the mesh number of the waste oil refining catalyst powder after the grinding is not less than 80 mesh, for example, 80 mesh, 100 mesh, 120 mesh or 200 mesh, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
As a preferred embodiment of the present invention, the persulfate solution includes any one or a combination of at least two of potassium persulfate solution, sodium persulfate solution, and ammonium persulfate solution, and the combination is typically, but not limited to, exemplified by: a combination of a potassium persulfate solution and a sodium persulfate solution, a combination of a sodium persulfate solution and ammonium persulfate, a combination of a potassium persulfate solution, a sodium persulfate solution and an ammonium persulfate solution, and the like.
As a preferred embodiment of the present invention, the solid-to-liquid ratio of the ground waste oil refining catalyst to the hydrogen peroxide solution or persulfate solution is not less than 1:5g/mL, for example, 1:5g/mL, 1:10g/mL, 1:20g/mL, 1:30g/mL, 1:35g/mL, 1:40g/mL, or 1:50g/mL, etc., but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
In a preferred embodiment of the present invention, the reaction temperature is 40 to 60 ℃, for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, etc., but the reaction temperature is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are similarly applicable.
In the present invention, the reaction temperature is extremely important for enhancing the effect of the reaction. If the temperature is too low, the strengthening effect cannot be achieved, and the oil removal rate is reduced; if the reaction temperature is too high, ineffective decomposition of hydrogen peroxide and persulfate occurs, resulting in non-targeted consumption of experimental raw materials and further reduced degreasing efficiency.
In a preferred embodiment of the present invention, the reaction time is 1 to 3 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 3 hours, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
As a preferable technical scheme of the invention, stirring is carried out in the reaction process.
In the invention, under the conditions of heating and stirring, the hydrogen peroxide and the persulfate can be fully contacted with the waste catalyst to carry out the strengthening reaction, so that the utilization rate of the hydrogen peroxide and the persulfate is improved while the reaction rate is improved.
As a preferable embodiment of the present invention, the solid-liquid separation is followed by drying.
As a preferred technical solution of the present invention, the method comprises the steps of:
mixing the ground waste oil refining catalyst with the mesh number not less than 80 with a hydrogen peroxide solution with the concentration of 5-15 wt% or a persulfate solution with the concentration of 50-100 mmol/L, stirring the mixture for 1-3 hours at the temperature of 40-60 ℃ with the solid-liquid ratio not less than 1:5g/mL, carrying out solid-liquid separation after reaction, and then drying to obtain the deoiled catalyst. Compared with the prior art, the invention has the following beneficial effects:
(1) The method utilizes metal ions in the waste oil refining catalyst to catalyze hydrogen peroxide or persulfate to generate Fenton-like effect, so that the surface oil quality of the waste oil refining catalyst is removed in an environment-friendly way, the whole treatment process is simple to operate, the equipment requirement is low, and the oil removal rate can reach more than 59.89 percent and up to 83.79 percent;
(2) The method disclosed by the invention takes hydrogen peroxide or persulfate as a reactant, does not introduce other impurities to pollute a sample, and avoids the problems of harmful gas generation in the oil removal process or environmental pollution caused by using an organic solvent, thereby being beneficial to industrial application.
Drawings
FIG. 1 is a process flow diagram of a method for removing oil from the surface of a spent refinery catalyst according to example 1 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
In one embodiment, the present invention provides a method for removing oil from the surface of a spent refinery catalyst, the method having a process flow chart as shown in FIG. 1, the method comprising the steps of:
mixing the ground waste oil refining catalyst with the mesh number not less than 80 with a hydrogen peroxide solution with the concentration of 5-15 wt% or a persulfate solution with the concentration of 50-100 mmol/L, stirring the mixture for 1-3 hours at the temperature of 40-60 ℃ with the solid-liquid ratio not less than 1:5g/mL, carrying out solid-liquid separation after reaction, and then drying to obtain the deoiled catalyst.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a method for removing oil on the surface of a waste oil refining catalyst, which comprises the following steps:
a spent hydrogenation catalyst from a domestic refinery is provided, wherein the mass fractions of various metals are respectively 0.88wt% of iron, 5.36wt% of nickel, 1.58wt% of molybdenum, 11.15wt% of aluminum and 17.77wt% of vanadium. The smoldering experiment proves that the average oil content of the spent oil refining catalyst is 16.3 percent. The contact angle of water drops measured on the surface of the waste oil refining catalyst after grinding and tabletting is 100.2 degrees, which shows that the surface property of the waste oil refining catalyst containing oil is hydrophobic.
2g of the ground waste oil refining catalyst (80 meshes) is mixed with 10mL of hydrogen peroxide solution with the concentration of 15wt%, and the mixture is stirred for 3 hours at 60 ℃ after being uniformly mixed by ultrasonic oscillation, the stirring speed is 400r/min, and the catalyst after deoiling is obtained after the reaction, filtration and drying.
Example 2:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 in that: the concentration of the hydrogen peroxide solution was 10wt% and the reaction temperature was 50 ℃.
Example 3:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 in that: the concentration of the hydrogen peroxide solution was 5wt% and the reaction temperature was 40 ℃.
Example 4:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 3 only in that: the reaction temperature was 30 ℃.
Example 5:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the stirring time was 2h.
Example 6:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the stirring time was 1h.
Example 7:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the stirring time was 0.5h.
Example 8:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the solution used was a potassium persulfate solution having a concentration of 100 mmol/L.
Example 9:
this example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the solution used was a potassium persulfate solution having a concentration of 50 mmol/L.
Example 10:
the embodiment provides a method for removing oil on the surface of a waste oil refining catalyst, which comprises the following steps:
a spent cracking catalyst from a refinery in China is provided, wherein the mass fractions of various metals are 27.62wt% of aluminum, 1.52wt% of iron, 2.31wt% of nickel and 3.43wt% of vanadium respectively. The average oil content of the spent refining catalyst is 12.6 percent through repeated verification of smoldering experiments. The contact angle of water drops measured on the surface of the waste oil refining catalyst after grinding and tabletting is 98.9 degrees, which shows that the surface property of the waste oil refining catalyst containing oil is hydrophobic.
2g of the ground waste oil refining catalyst (100 meshes) is mixed with 10mL of hydrogen peroxide solution with the concentration of 15wt%, and the mixture is stirred for 3 hours at 60 ℃ after being uniformly mixed by ultrasonic oscillation, the stirring speed is 400r/min, and the catalyst after deoiling is obtained after the reaction, filtration and drying.
Example 11:
the embodiment provides a method for removing oil on the surface of a waste oil refining catalyst, which comprises the following steps:
a spent reforming catalyst from a refinery in China is provided, wherein the mass fractions of various metals are 90.7wt% of aluminum, 0.13wt% of iron, 0.71wt% of titanium and 0.39wt% of rhenium, respectively. The average oil content of the spent refining catalyst is 9.3 percent through repeated verification of smoldering experiments. The waste catalyst is bonded by large block particles, and the surface of the waste catalyst is black and oily to the naked eye. After grinding and tabletting, the contact angle of water drops is measured at the surface of the catalyst to be 99.3 degrees, which shows that the surface of the oil-containing spent catalyst is hydrophobic.
2g of the ground waste oil refining catalyst (80 meshes) is mixed with 10mL of hydrogen peroxide solution with the concentration of 15wt%, and the mixture is stirred for 3 hours at 60 ℃ after being uniformly mixed by ultrasonic oscillation, the stirring speed is 400r/min, and the catalyst after deoiling is obtained after the reaction, filtration and drying.
Comparative example 1:
this comparative example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the spent refinery catalyst is not ground.
Comparative example 2:
this comparative example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the concentration of the hydrogen peroxide solution was 20wt%.
Comparative example 3:
this comparative example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 3 only in that: the concentration of the hydrogen peroxide solution was 3wt%.
Comparative example 4:
this comparative example provides a method for removing oil from the surface of a spent refinery catalyst, which is different from the method of example 1 only in that: the solution used was a potassium persulfate solution having a concentration of 30 mmol/L.
The surface water drop contact angles of the deoiled catalysts of examples 1 to 11 and comparative examples 1 to 4 were measured, and the oil removal rates were calculated as shown in table 1, wherein the calculation formula is shown in formula (1):
TABLE 1
Contact angle/° Oil removal rate/%
Example 1 59.4 83.79
Example 2 67.8 76.37
Example 3 76.8 62.79
Example 4 85.9 51.44
Example 5 62.6 80.87
Example 6 82.3 60.33
Example 7 87.1 46.80
Example 8 60.3 81.71
Example 9 83.0 59.89
Example 10 66.7 77.27
Example 11 68.7 75.45
Comparative example 1 89.6 39.07
Comparative example 2 85.2 52.33
Comparative example 3 88.1 41.15
Comparative example 4 87.9 42.31
As can be seen from table 1, the method of the invention is adopted in examples 1-3, 5-6 and 8-11, the contact angle of water drops on the surface of the catalyst subjected to oil removal treatment is reduced to less than 83 degrees, the minimum contact angle can be reduced to less than 59.4 degrees, the surface becomes hydrophilic, the wettability is obviously changed, the oil removal efficiency is as high as more than 59.89%, and the oil removal process is realized by catalyzing hydrogen peroxide or persulfate to produce Fenton-like reaction; compared with example 3, the reaction temperature of example 4 is too low, and as can be seen from the change of the contact angle, the change of the surface wettability of the spent catalyst after the oil removal treatment is not obvious, and the oil removal efficiency is low; example 7 has a shorter reaction time than example 6, and does not sufficiently remove the oil in the spent catalyst.
In comparative example 1, the spent refinery catalyst was not ground, resulting in a small contact area of the catalyst with the solution, greatly affecting the oil removal efficiency, only 39.07%.
As can be seen from comparative examples 2 to 4, if the concentration of the hydrogen peroxide solution used is too high, ineffective decomposition of hydrogen peroxide and persulfate occurs, resulting in non-targeted consumption of experimental raw materials and thus reduced oil removal rate; if the concentration of the hydrogen peroxide solution or the persulfate solution is too low, the oil removal reaction effect is poor, and the aim of high-efficiency oil removal cannot be achieved.
It can be seen from the above examples and comparative examples that the method of the invention utilizes metal ions in the spent oil refining catalyst to catalyze hydrogen peroxide or persulfate to generate Fenton-like effect, thereby removing oil on the surface of the spent oil refining catalyst in an environment-friendly manner, the whole treatment process is simple to operate, the requirement on equipment is low, and the oil removal rate can reach more than 59.89 percent and can reach 83.79 percent at most; in addition, the method takes hydrogen peroxide or persulfate as a reactant, does not introduce other impurities to pollute a sample, avoids the problem of harmful gas generated in the oil removal process or environmental pollution caused by using an organic solvent, and is beneficial to industrial application.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for operation of the present invention, addition of auxiliary operations, selection of specific modes, etc., are intended to fall within the scope of the present invention and the scope of the disclosure.

Claims (5)

1. A method for removing oil from the surface of a spent refinery catalyst, said method comprising the steps of:
mixing the ground waste oil refining catalyst with a hydrogen peroxide solution or a persulfate solution, and performing solid-liquid separation after reaction to obtain a deoiled catalyst;
the waste oil refining catalyst comprises one or a combination of at least two of a desulfurization hydrogenation catalyst, a catalytic cracking catalyst and a catalytic reforming catalyst; after grinding, the mesh number of the waste oil refining catalyst powder is not less than 80 meshes;
the concentration of the hydrogen peroxide solution is 5-15wt%;
the concentration of the persulfate solution is 50-100 mmol/L;
the solid-liquid ratio of the ground waste oil refining catalyst to the hydrogen peroxide solution or the persulfate solution is not less than 1:5g/mL;
the temperature of the reaction is 42-60 ℃; the reaction time is 1-3 h.
2. The method of claim 1, wherein the milling is performed using an agate mortar.
3. The method of claim 1, wherein the persulfate solution comprises any one of a potassium persulfate solution, a sodium persulfate solution, or a ammonium persulfate solution, or a combination of at least two.
4. The method of claim 1, wherein stirring is performed during the reaction.
5. The method of claim 1, wherein the solid-liquid separation is followed by drying.
CN202210207554.3A 2022-03-04 2022-03-04 Method for removing oil on surface of waste oil refining catalyst Active CN114522699B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210207554.3A CN114522699B (en) 2022-03-04 2022-03-04 Method for removing oil on surface of waste oil refining catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210207554.3A CN114522699B (en) 2022-03-04 2022-03-04 Method for removing oil on surface of waste oil refining catalyst

Publications (2)

Publication Number Publication Date
CN114522699A CN114522699A (en) 2022-05-24
CN114522699B true CN114522699B (en) 2023-10-27

Family

ID=81626315

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210207554.3A Active CN114522699B (en) 2022-03-04 2022-03-04 Method for removing oil on surface of waste oil refining catalyst

Country Status (1)

Country Link
CN (1) CN114522699B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117654995A (en) * 2024-01-31 2024-03-08 西部鑫兴稀贵金属有限公司 Ultrasonic pretreatment method for molybdenum-series spent catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004067453A1 (en) * 2003-01-31 2004-08-12 Idemitsu Kosan Co., Ltd. Method of treating wastewater containing hardly decomposable harmful substances
CN102020350A (en) * 2011-01-04 2011-04-20 华中师范大学 Processing method of heterocatalysis persulfate Fenton oxidation water
CN103359820A (en) * 2012-03-30 2013-10-23 中国石油化工股份有限公司 Method for treatment on wastewater by adopting oil refining waste catalyst for catalytic oxidation
CN105498860A (en) * 2016-01-30 2016-04-20 清华大学 Method for deoiling oil-bearing waste catalyst
CN108160694A (en) * 2017-12-26 2018-06-15 北京宜为凯姆环境技术有限公司 For the complex activation method of the persulfate of environment remediation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004067453A1 (en) * 2003-01-31 2004-08-12 Idemitsu Kosan Co., Ltd. Method of treating wastewater containing hardly decomposable harmful substances
CN102020350A (en) * 2011-01-04 2011-04-20 华中师范大学 Processing method of heterocatalysis persulfate Fenton oxidation water
CN103359820A (en) * 2012-03-30 2013-10-23 中国石油化工股份有限公司 Method for treatment on wastewater by adopting oil refining waste catalyst for catalytic oxidation
CN105498860A (en) * 2016-01-30 2016-04-20 清华大学 Method for deoiling oil-bearing waste catalyst
CN108160694A (en) * 2017-12-26 2018-06-15 北京宜为凯姆环境技术有限公司 For the complex activation method of the persulfate of environment remediation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘希涛等.《活化过硫酸盐在环境污染控制中的应用》.中国环境科学出版社,2018,第56-57页. *
吴功德等.《环境催化基础及应用》.中国环境出版集团,2019,第298-301页. *

Also Published As

Publication number Publication date
CN114522699A (en) 2022-05-24

Similar Documents

Publication Publication Date Title
CN102451774B (en) Method for regenerating inactivated hydrotreating catalyst
Bharadwaj et al. Bioleaching of spent hydrotreating catalyst by acidophilic thermophile Acidianus brierleyi: Leaching mechanism and effect of decoking
CN114522699B (en) Method for removing oil on surface of waste oil refining catalyst
Pradhan et al. A novel sequential process of bioleaching and chemical leaching for dissolving Ni, V, and Mo from spent petroleum refinery catalyst
Muddanna et al. Leaching of nickel and vanadium from the spent fluid catalytic cracking catalyst by reconnoitering the potential of Aspergillus niger associating with chemical leaching
CN102310005A (en) Regeneration method for heavy oil hydro-treating catalyst
Wang et al. Ultrasound-assisted oil removal of γ-Al2O3-based spent hydrodesulfurization catalyst and microwave roasting recovery of metal Mo
CN114606386B (en) Process for recovering cobalt and lithium by grinding and leaching waste lithium battery
CN105274346A (en) Aluminum ash recycling process
CN113789446A (en) Method for recovering molybdenum, vanadium and nickel metals from waste catalyst
CN111628202B (en) VOSO4Preparation method of sulfuric acid solution and VOSO4Electrolyte solution
CN111690429A (en) Supercritical hydrothermal viscosity reduction method for oil sand asphalt
CN106902896A (en) A kind of method for removing aluminium scrap base hydrogenation catalyst surface oily substance
Nie et al. Eco-friendly strategy for advanced recycling waste copper from spent lithium-ion batteries: preparation of micro-nano copper powder
CN101875853A (en) Non-hydrogenation refining method for coking waxy oil
CN101613804B (en) Method for recovering cadmium from waste nickel-cadmium battery
CN108423952B (en) Combined process for treating oily sludge by supercritical fluid gradient extraction-oxidative degradation coupling
CN110157478B (en) Pretreatment method of coal tar raw material
CN112960882B (en) Treatment method of oily solid and utilization method of oily sludge containing oily solid
CN108531208A (en) A method of drawing off agent catalytic pyrolysis high-molecular compound using FCC
Marafi et al. Utilization of waste spent hydroprocessing catalyst: development of a process for full recovery of deposited metals and alumina support
CN103769135B (en) A kind of preparation method of isobutene partial oxidation MAL catalyst
Srichandan et al. Microbial extraction metal values from spent catalyst: Mini review
CN114134328B (en) Method for extracting vanadium and chromium from vanadium and chromium containing mud through catalytic oxidation by using alkali medium
CN112746170B (en) Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier

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