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CN109158100A - A kind of catalyst and preparation method thereof of catalytic cracking waste-plastic production fuel oil - Google Patents

A kind of catalyst and preparation method thereof of catalytic cracking waste-plastic production fuel oil Download PDF

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CN109158100A
CN109158100A CN201811142540.8A CN201811142540A CN109158100A CN 109158100 A CN109158100 A CN 109158100A CN 201811142540 A CN201811142540 A CN 201811142540A CN 109158100 A CN109158100 A CN 109158100A
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catalyst
clay
preparation
weight
solution
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CN109158100B (en
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王中慧
卢欢亮
汪永红
李朝晖
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GUANGDONG PROVINCIAL ACADEMY OF ENVIRONMENTAL SCIENCE
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GUANGDONG PROVINCIAL ACADEMY OF ENVIRONMENTAL SCIENCE
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    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention is a kind of catalyst of catalytic cracking waste-plastic production fuel oil, metallic catalyst including modified column clay and its load, the modified column clay is prepared by montmorillonite race or kaolin group, the metallic catalyst has included the transistion metal compound and nontransition metal compound of catalytic action, and the weight of transistion metal compound accounts for 95% or more of the weight of the metallic catalyst.Catalyst of the invention has suitable acidity and good characteristic, decomposition efficiency is high, have to production of diesel fuels highly selective, without being sorted before pyrolysis, reduce the operating cost of manpower and relevant device, the catalyst can be used for the catalytic pyrolysis of mixed plastic raw material and hydrocarbon materials, be suitable for various types of pyrolysis reactors such as fluidized-bed reactor, tubular reactor, reacting in rotary kiln device, stirred tank reactor, auger conveyor.

Description

A kind of catalyst and preparation method thereof of catalytic cracking waste-plastic production fuel oil
Technical field
The present invention relates to a kind of methods using waste recovery resource, and in particular to a kind of catalytic cracking waste-plastic production Catalyst of fuel oil and preparation method thereof.
Background technique
Plastics are widely used high molecular materials, and China just became the big plastics country of consumption of the first in the world from 2011, And a large amount of waste plastics cause " white pollution " got worse, and very more pressure is brought to the environmental protection in China.It is right For waste plastics, traditional processing method of disposal have landfill, burning, regeneration, renewable resources, replaced with degradation plastic it is existing Have the technologies such as plastics, with waste plastics amount year by year increase and environmental protection management it is increasingly strict, landfill and burning disposal start by It is even resisted to limitation, therefore is a kind of preferable processing method using waste plastics preparing liquid fuel, this method is more suitble to China's national situation can not only handle white pollution, but also resource can be obtained.But producing fuel oil using waste plastics Direct Pyrolysis, there are quantity of slag mistakes Greatly, the problems such as coking problem, catalytic efficiency be low.
CN 104611060B discloses a kind of method using waste plastics and Gao Fang component production clean fuel oil, Gao Fang After component is mixed with converting plastic waste to oil, heat scission reaction area is first passed through, heat scission reaction area uses and is gradually warmed up and constant temperature method phase In conjunction with mode；It obtains cracking gas and enters back into catalytic reaction zone, generation catalysis reaction, gained reaction are contacted with catalyst therein Effluent obtains gaseous product and liquid phase oil product into gas-liquid separation is carried out.Technical solution reaction catalyst used is HY boiling Any one in stone, Ni-REY zeolite, HZSM-5 zeolite, HC-1 molecular sieve catalyst and amorphous silica-alumina SiO2-Al2O3 Or it is two or more, dosage is the 0.5%~2.0% of general waste plastics and Gao Fang component weight, but catalyst efficiency is not Height, and reaction step is cumbersome, and technics comparing is complicated.
CN108456328A discloses a kind of processing method of waste plastics, and specifically disclosing the modified catalyst is to change Property agent oxide modifying HZSM-5 and HY complex type molecular sieve, modifying agent is selected from one of Sn, Fe, Ti and Zn or a variety of, The reaction dissolvent is the mixture of tetrahydronaphthalene and hexadecane.The technical solution is in the premise for guaranteeing to have higher conversion Under significantly reduce the temperature of waste plastics catalytic pyrolysis, saved energy consumption.But plastics is inefficient, selectivity is not It is good, it handles relatively complicated.
To sum up, the prior art still lacks a kind of catalyst that can handle various waste plastics and energy high efficiency acquisition fuel oil.
Summary of the invention
The first purpose of this invention is to develop a kind of catalyst for capableing of catalytic cracking waste-plastic production fuel oil, energy The organic wastes such as various waste plastics are handled, efficient-decomposition is fuel oil, and yield and selectivity are higher.Of the invention is detailed Technical solution is as follows.
A kind of catalyst for capableing of catalytic cracking waste-plastic production fuel oil, the gold including modified column clay and its load Metal catalyst, the modified column clay are prepared by montmorillonite race or kaolin group, and the montmorillonite race includes swelling Soil, saponite, montmorillonite, the kaolin group include kaolinite and/or galapectite, and the particle size of the modified column clay is 20 μm or less, average pore size is 50nm or more, BET surface area 100-400m2/g；
The metallic catalyst has included the transistion metal compound and nontransition metal compound of catalytic action, transition gold The weight of category compound accounts for 95% or more of the weight of the metallic catalyst, the transition metal in the transistion metal compound Metallic element including Group IIB, Group IVB and VIII group, transistion metal compound is with the shape of hydrochloride, silver nitrate and sulfate Formula exists；
The molar ratio of silica and aluminium oxide is 4-50:1 in the modified column clay, and the quality of the aluminium oxide accounts for The quality of the 2-26% of total catalyst weight, the silica account for the 45-87wt% of total catalyst weight, metallic catalyst Quality accounts for the 10-35% of total catalyst weight.
Catalyst of the invention has two o'clock different with conventional catalyst.First, the carrier of catalyst is that modification is pillared Clay, and further limiting particle size is 20 μm hereinafter, average pore size is 50nm or more, BET surface area 100-400m2/ G, compared with common zeolite based catalysts and medium-pore catalyst, aperture is larger, and overcracking is inclined to lower, high catalytic efficiency, Selectivity is strong, and due to more mildly, having suitable acidity for the pillared clay-phase ratio of modification, can prepare high-quality Diesel oil.Second, the type of catalyst is more, can obtain preferable catalytic effect.Especially iron family element and zinc family elements The diesel oil of high-quality can be obtained.
Preferably, the particle size of the modified column clay is 15 μm hereinafter, average pore size is 100nm or more, BET Surface area is 200-400m2/ g, the transition metal in the transition-metal catalyst include the metal member of VIII group and Group IIB Element.The size for further limiting matrix improves the catalytic efficiency of catalyst.
Preferably, the transition metal in the transition-metal catalyst includes ferro element, the ferro element catalyst Quality accounts for the 10-35% of total catalyst weight.The efficiency of ferrum-based catalyst be it is extraordinary, resolution ratio is in all metallic elements It is highest.
Preferably, further include the Zn-ef ficiency of Group IIB transition metal in the transition-metal catalyst, the ferro element Weight accounts for the 10-30% of total catalyst weight, and the weight of the Zn-ef ficiency accounts for total catalyst weight 5-10%.Iron zinc catalyst phase Mutually cooperation can improve the C distribution in diesel oil, obtain the diesel oil of high-quality.
A second object of the present invention is to provide a kind of preparation methods of above-mentioned catalyst, which is characterized in that including with Under several steps:
(1) it pre-processes: clay raw material is ground to average-size no more than 30 mesh；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: mixing using alkaline solution as activator with transition metal chemistry object, mixed solution PH control is 1-4.5, and after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 15-95 DEG C, and time for adding control is 2-20 hours；
(5) aging and washing: by the solution after step (4) intercalation 15-75 DEG C at a temperature of aging 6-24 hours, aging Afterwards, washed repeatedly with distilled water or deionized water, with remove chloride ion present in clay, nitrate ion or sulfate radical from Son obtains clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 40-80 DEG C at a temperature of it is 5-20 hours dry, be modified Column clay precursor；
(7) calcine: temperature lower calcination of the column clay precursor that step (6) is obtained at 300-600 DEG C obtains pillared viscous Native catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is at any shape in little particle, pellet, sphere Formula, to adapt to the different needs of different pyrolysis reactors.
For the present invention by adjusting i.e. clay, the ratio of metallic compound and parameter during intercalation adjust the catalysis The acid strength and texture attribute of agent.Adjustable acid strength and quality structure allow the catalyst to adapt to different material conditions Or different plastic raw materials form (mixtures of i.e. certain types of plastics or several particular plastic types), can obtain difference Diesel product and/or different proportion gasoline and diesel oil.
Preferably, in the step (4), transition gold in the quality of the clay in the step (1) and the step (3) The mass ratio for belonging to compound is 1-5:1.
Preferably, stabilizer can be added in the step (4), the stabilizer is Dodecyl Dimethyl Amine, benzene Prick one of bromine ammonium, diallyl dimethyl ammoniumchloride and cationic polyacrylamide.Intercalation can be improved in stabilizer Stability, and then improve the catalytic efficiency of catalyst.
Third object of the present invention provides the application of the catalyst, and the catalyst can be used for mixed plastic raw material With the catalytic pyrolysis of hydrocarbon materials, the mixed plastic raw material include polyethylene (PE), polypropylene (PP), polystyrene (PS), Polyethylene terephthalate (PET), polyvinyl chloride (PVC) etc., the hydrocarbon materials include wax, tar and heavy oil etc..This Invention is capable of handling mixed plastic waste, without being sorted before pyrolysis, while keeping the liquid hydrocarbon of high yield.It does not need pre- Sorting process reduces the operating cost of manpower and relevant device, therefore is conducive to large-scale application pyrolysis and is used as plastic wastes again Round-robin method.
Preferably, the use of the reaction temperature that the catalyst is pyrolyzed being 350-600 DEG C.Catalyst of the invention is anti- It answers temperature lower, energy consumption can be reduced by reaction temperature and time needed for reducing mixed plastic fraction pyrolysis, save energy Source.
Preferably, the catalyst is suitable for fluidized-bed reactor, tubular reactor, reacting in rotary kiln device, stirred tank Various types of pyrolysis reactors such as reactor, auger conveyor.The present invention is suitable for a variety of reaction vessels, can answer on a large scale For different occasion treatment of waste plastics.
The beneficial effects of the present invention are as follows:
(1) catalyst of the invention has suitable acidity and good characteristic, and decomposition efficiency is high, to production of diesel fuels With highly selective, without being sorted before pyrolysis, the operating cost of manpower and relevant device is reduced, therefore be conducive to big Sizable application pyrolysis is used as plastic wastes method for recycling.
(2) catalyst of the invention is compared with common zeolite based catalysts and medium-pore catalyst, due to the catalyst Mild and suitable acidity, overcracking tendency it is lower；The thermal stability of catalyst is high, is loaded into long-time operation viscous Transition metal loss reduction on soil.
(3) catalyst of the invention passes through the ratio of fine tuning raw material and the parameter during intercalation adjusts the catalyst Acid strength and texture attribute, the pyrolysis gas that different proportion may be implemented is as needed, obtains diesel oil and the combustion of different cultivars Material oil.
(4) reaction temperature needed for catalyst of the invention urges part to decompose waste plastics is lower, less energy consumption needed for reacting, cost Lower than common zeolite based catalysts and medium-pore catalyst, it is suitable for a variety of reaction vessels, it can be with large-scale application in different fields Close treatment of waste plastics.
Specific embodiment
Prepare embodiment
In the preparation embodiment, clay raw material used are selected from the bentonite of Sigma-Aldrich (USA), particle ruler Very little is 15 μm or less, and average pore size is 100nm or more, BET surface area 200-400m2/g。
Embodiment 1: Ti-base catalyst (Ti)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) it the preparation of intercalation solution: is mixed the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 2g titanium chloride It closes, the pH control of mixed solution is 4, and after mixing, making solution, aging 4h reaches balance at a certain temperature；
(4) intercalation: under agitation, it is viscous that intercalation solution prepared by step (3) is added drop-wise to the homogeneous that step (2) obtains In native suspension, dropping temperature control is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water washs repeatedly, to remove chloride ion present in clay, obtains clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 2: Zirconium-base catalyst (Zr)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) it the preparation of intercalation solution: is mixed the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 2g zirconium chloride It closes, the pH control of mixed solution is 4, and after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 3: ferrum-based catalyst (Fe)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: chlorine is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six Change iron mixing, the pH control of mixed solution is 4, and after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 4: cobalt-base catalyst (Co)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: nitre is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six The pH control of sour cobalt mixing, mixed solution is 4, and after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 5: nickel-base catalyst (Ni)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: nitre is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six The pH control of sour nickel mixing, mixed solution is 4, and after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 6: zinc based catalyst (Zn)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: nitre is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six The pH control of sour zinc mixing, mixed solution is 4, and after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 7: iron zinc composite catalyst (Fe/Zn)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: chlorine is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 3g six Change iron and the mixing of 3g zinc nitrate hexahydrate, the pH control of mixed solution is 4, after mixing, makes solution aging one at a certain temperature The section time reaches balance；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 8: iron zinc composite catalyst (Fe/Zn)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: chlorine is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six Change iron and the mixing of 2g zinc nitrate hexahydrate, the pH control of mixed solution is 4, after mixing, makes solution aging one at a certain temperature The section time reaches balance；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 9: iron zinc composite catalyst (Fe/Zn)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: chlorine is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six Change iron and the mixing of 2g zinc nitrate hexahydrate, the pH control of mixed solution is 4, after mixing, makes solution aging one at a certain temperature The section time reaches balance；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Embodiment 10: iron zinc composite catalyst (Fe/Zn)
(1) it pre-processes: 10g clay raw material being ground to average-size no more than 30 mesh, is selected from Sigma-Aldrich (USA) raw material of the bentonite as caly structure；
(2) preparation of homogeneous slurry: the clay that step (1) obtains is mixed with deionized water under stiring Homogeneous slurry；
(3) preparation of intercalation solution: chlorine is hydrated using the alkaline solution of sodium hydroxide of 0.1mol/L as activator and 4g six Change iron and the mixing of 1g zinc nitrate hexahydrate, the pH control of mixed solution is 4, after mixing, makes solution aging one at a certain temperature The section time reaches balance；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and is dripped The control of heating degree is 80 DEG C, and time for adding control is 15 hours；
(5) aging and washing: by the solution after step (4) intercalation 60 DEG C at a temperature of aging 24 hours, after aging, use Distilled water or deionized water are washed repeatedly, to remove chloride ion present in clay, obtain clay slurry after washing；
(6) dry: the clay slurry that step (5) is obtained 80 DEG C at a temperature of it is 10 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: the column clay precursor that step (6) is obtained obtains column clay in 500 DEG C of temperature lower calcination 6h Catalyst；
(8) form: the column clay catalyst preparation that step (7) are obtained is stand-by at powder.
Comparative example
The application chooses common concentrated catalyst embodiment as a comparison.Including 1 zeolite based catalysts of comparative example ZSM-5,2 medium-pore catalyst Zr-MCM-41 of comparative example, 3 medium-pore catalyst Al-SBA-15 of comparative example and comparison are implemented 4 medium-pore catalyst Fe-SBA-15 of example.
Application Example
Test efficiency of the catalyst of synthesis in the catalytic pyrolysis of mixed plastic.
The raw material used in all Pyrolysis Experiments is polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly- pair The mixture of ethylene terephthalate (PET), ratio (PE:PP:PS:PET) are 42:35:18:5.Wherein, sample P E is (close Degree: 0.95g/cm3), PP (density: 0.9g/cm3) and PET (density: 1.3-1.4g/cm3) be in granular form, nominal particle size is 3mm, and PS (density: 1.05g/cm3) it is powder type, average grain diameter is 250 μm.Granular PE is purchased from Alfa Aesar (USA), And PP, PET and PS are purchased from Goodfellow Cambridge Ltd (UK).
Other than using ZSM-5, all catalytic pyrolysis experiments are carried out using the horizontal tube reactor not stirred.? In each experiment, by 10g mixed plastic raw material (PE:PP:PS:PET=42:35:18:5) with catalyst (powder type) anti- It answers in container and mixes, horizontal tube reactor is heated to 500 DEG C with the heating speed of 10 DEG C/min.By nitrogen with 200ml/ The flow velocity of min is added in reactor to generate inert environments, and gaseous state and liquid product are purged out reactor, then by liquid Product is condensed and is collected in oil interceptor.
1 catalyst Z SM- of comparative example uses the tubular reactor not stirred, 100g raw material, the nitrogen of 1000ml/min (N2) flow (being enough gaseous state and liquid product purging out reactor) and reaction temperature be 500 DEG C (heating rate: 20 DEG C/ min).The mass ratio (C/F) of catalyst and waste plastics, commonly used in range of the C/F ratio 0.1 to 1 of clay-based catalyst It is interior, and the common C/F ratio of zeolite based catalysts and medium-pore catalyst is in the range of 0.01 to 0.5.Generally, due to lower In the acidity and weaker cracking activity of clay-based catalyst, the C/F ratio for clay-based catalyst is higher than based on zeolite The C/F of catalyst and medium-pore catalyst ratio, to provide enough catalytic activity for pyrolysis.
After carrying out preliminary Pyrolysis Experiment several times with the clay-based catalyst of various dose, when C/F ratio is more than 0.3, see Observe oil yield reduction, it may be possible to due to excessively cracking.Therefore, for all catalyst experiments based on clay, 0.3 is selected C/F ratio, to ensure enough catalytic activity while avoid excessively cracking.On the other hand, Fe-SBA-15 and other mesoporous are found The best C/F ratio of catalyst (Al-MCM-41, Zr-MCM-41 and Al-SBA-15) is respectively 0.05 and 0.03.The fuel measured The weight ratio of diesel oil is as shown in table 1 in oil yield and fuel oil.
The catalytic efficiency of 1 different catalysts of table
The data of analytical table 1 are it is found that first, (including the boiling of the modification column clay of the application and other clay-based catalyst Ground mass and conventional aluminium column clay) it compares, with high oil productivity and high diesel oil selectivity, and zeolite based catalysts and mesoporous Catalyst tends to lead to low oil yield and/or the poor selectivity to diesel oil distillate, is attributable to peracidity property and catalysis The small-bore of agent causes excessively to crack, and C chain shortens, transition cracking.Second, various metals catalyst in the application, the catalysis of iron Effect is more than 70%, selectivity is also highest, and the catalytic effect of zinc is best, and selectivity is inferior to iron.Third, although this Shen Please C/F it is higher compared to existing catalyst, catalyst is larger using quantitative change, but the cost of column clay is urged well below other Agent carrier, the catalyst use cost of the application is lower for Comprehensive Correlation.
It is by going to measure on the basis of Cetane number that usually we, which evaluate high-quality diesel oil,.Cetane number is higher, shows bavin The ignition quality of oil is good, delay period is short, combustion even, engine start are steady.Cetane number is low, shows that burning ignition is difficult, Delay period is long, and engine behavior is rough.But Cetane number is excessively high, will also be generated few due to local imperfect combustion Measure black smoke evacuation.The Cetane number of diesel oil is related with its chemical composition and fractional composition.In the identical various diesel oil of carbon atom number In component hydro carbons, the Cetane number highest of n-alkane, the Cetane number of condensed-nuclei aromatics is minimum, and alkene, cycloalkane are between alkane Between aromatic hydrocarbons.The isomery degree of hydro carbons is higher, and number of rings is more, and Cetane number is lower；Cycloalkane and aromatic hydrocarbon are with band side chain The increase of length, Cetane number increase therewith, and increasing with side chain branch, Cetane number are reduced therewith.
Therefore, on the basis of above-mentioned experiment, the application continues mover iron zinc composite catalyst (Fe/Zn), is expected to obtain The diesel oil of higher quality.According to same application implementation mode, the application is multiple to iron zinc prepared by embodiment 7- embodiment 10 It closes catalyst (Fe/Zn) to have carried out using testing, the mass ratio (C/F) of catalyst and waste plastics is 0.3, and the fuel oil measured produces The weight ratio, Cetane number of diesel oil are as shown in table 2 in rate and fuel oil.
The catalytic efficiency of 2 iron zinc composite catalyst of table
As shown in Table 2, first, iron zinc composite catalyst compares individual ferrum-based catalyst and zinc based catalyst catalytic efficiency Higher with selectivity, the accounting of iron more high yield is higher, and metallic element not of the same clan produces catalyzing cooperation effect between iron zinc, Second, iron zinc composite catalyst compares individual ferrum-based catalyst and zinc based catalyst, and octane number is effectively improved, generally The Cetane number of diesel engine fuel oil is within the scope of 40~55, and therefore, the diesel oil that iron zinc composite catalyst obtains more has city Field prospect.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to the one of invention A little modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.

Claims (10)

1. a kind of catalyst of catalytic cracking waste-plastic production fuel oil, which is characterized in that including modified column clay and its bear The metallic catalyst of load, the modified column clay are prepared by montmorillonite race or kaolin group, the montmorillonite race packet Bentonite, saponite, montmorillonite are included, the kaolin group includes kaolinite and/or galapectite, the particle of the modified column clay Having a size of 20 μm or less, average pore size is 50nm or more, BET surface area 100-400m2/g；
The metallic catalyst has included the transistion metal compound of catalytic action and the nontransition metal for not playing catalytic action Object is closed, the weight of transistion metal compound accounts for 95% or more of the weight of the metallic catalyst, the transistion metal compound In transition metal include Group IIB, Group IVB and VIII group metallic element, transistion metal compound with hydrochloride, silver nitrate and The form of sulfate exists；
The molar ratio of silica and aluminium oxide is 4-50:1 in the modified column clay, and the quality of the aluminium oxide accounts for catalysis The 2-26% of agent total weight, the quality of the silica account for the 45-87wt% of total catalyst weight, the quality of metallic catalyst Account for the 10-35% of total catalyst weight.
2. a kind of catalyst as described in claim 1, which is characterized in that the particle size of the modified column clay is 15 μm Hereinafter, average pore size is 100nm or more, BET surface area 200-400m2/ g, the transition gold in the transition-metal catalyst Belong to the metallic element including VIII group and Group IIB.
3. a kind of catalyst as claimed in claim 2, which is characterized in that the transition metal packet in the transition-metal catalyst Ferro element is included, the quality of the ferro element catalyst accounts for the 10-35% of total catalyst weight.
4. a kind of catalyst as claimed in claim 3, which is characterized in that further include zinc member in the transition-metal catalyst Element, the weight of the ferro element account for the 10-30% of total catalyst weight, and the weight of the Zn-ef ficiency accounts for total catalyst weight 5- 10%.
5. a kind of preparation method of such as catalyst of any of claims 1-4, which is characterized in that including following Step:
(1) it pre-processes: clay raw material is ground to average-size no more than 30 mesh；
(2) clay that step (1) obtains the preparation of homogeneous slurry: is mixed with homogeneous with deionized water under stiring Slurry；
(3) preparation of intercalation solution: mixing using alkaline solution as activator with transition metal chemistry object, the pH control of mixed solution It is made as 1-4.5, after mixing, making solution, aging reaches balance for a period of time at a certain temperature；
(4) intercalation: intercalation solution prepared by step (3) is added drop-wise in the homogeneous slurry that step (2) obtains, and temperature is added dropwise Degree control is 15-95 DEG C, and time for adding control is 2-20 hours；
(5) aging and washing: by the solution after step (4) intercalation 15-75 DEG C at a temperature of aging 6-24 hours, after aging, It is washed with distilled water or deionized water, to remove chloride ion present in clay, nitrate ion or sulfate ion, is washed repeatedly Clay slurry is obtained after washing；
(6) dry: the clay slurry that step (5) is obtained 40-80 DEG C at a temperature of it is 5-20 hours dry, obtain being modified pillared Clay precursor；
(7) calcine: temperature lower calcination of the column clay precursor that step (6) is obtained at 300-600 DEG C obtains column clay and urges Agent；
(8) form: the column clay catalyst preparation that step (7) are obtained at any form in little particle, pellet, sphere, To adapt to the different needs of different pyrolysis reactors.
6. a kind of preparation method of catalyst as claimed in claim 5, which is characterized in that the matter of clay in the step (1) Amount and the mass ratio of transistion metal compound in the step (3) are 1-5:1.
7. a kind of preparation method of catalyst as claimed in claim 5, which is characterized in that in the step (4), can be added steady Determine agent, the stabilizer is that Dodecyl Dimethyl Amine, benzalkonium bromide, diallyl dimethyl ammoniumchloride and cation are poly- One of acrylamide.
8. a kind of application of such as catalyst of any of claims 1-4, which is characterized in that the catalyst can be used for The catalytic pyrolysis of mixed plastic raw material and hydrocarbon materials, the mixed plastic raw material include polyethylene (PE), polypropylene (PP), gather Styrene (PS), polyethylene terephthalate (PET), polyvinyl chloride (PVC) etc., the hydrocarbon materials include wax, tar With heavy oil etc..
9. a kind of application of catalyst as claimed in claim 8, which is characterized in that be pyrolyzed using the catalyst anti- Answering temperature is 350-600 DEG C.
10. a kind of application of catalyst as claimed in claim 8, which is characterized in that it is anti-that the catalyst is suitable for fluidized bed Answer various types of pyrolysis reactors such as device, tubular reactor, reacting in rotary kiln device, stirred tank reactor, auger conveyor.
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