CN110343539A - A kind of method of dual catalyst catalytic pyrolysis waste tire - Google Patents

A kind of method of dual catalyst catalytic pyrolysis waste tire Download PDF

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Publication number
CN110343539A
CN110343539A CN201910653370.8A CN201910653370A CN110343539A CN 110343539 A CN110343539 A CN 110343539A CN 201910653370 A CN201910653370 A CN 201910653370A CN 110343539 A CN110343539 A CN 110343539A
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CN
China
Prior art keywords
catalyst
tio
silica wool
zno
zsm
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Pending
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CN201910653370.8A
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Chinese (zh)
Inventor
王黎
覃刘平
李钰琦
鲁逸飞
胡宁
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Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
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Wuhan University of Science and Engineering WUSE
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Priority to CN201910653370.8A priority Critical patent/CN110343539A/en
Publication of CN110343539A publication Critical patent/CN110343539A/en
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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
    • B01J23/06—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
    • 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
    • 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
    • C10G1/008—Controlling or regulating of liquefaction processes
    • 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
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of methods of dual catalyst catalytic pyrolysis waste tire, describe ZnO-TiO2The preparation method of ZSM-5 molecular sieve catalyst after catalyst and NaOH hydrothermal modification.Silica wool → ZSM-5 → silica wool → ZnO-TiO is used simultaneously2→ silica wool → raw material → silica wool → ZnO-TiO2→ silica wool → ZSM-5 → silica wool quartz ampoule filling sequence, the method for dual catalyst heating cracking waste-tyre rubber-powder.Waste tire thermal cracking required temperature can be effectively reduced, effectively reduce coking or the generation of carbon deposition phenomenon in pyrolytic process, there is apparent selectivity for the generation of aromatic hydrocarbons in cracking oil product, the concentration of benzene,toluene,xylene, naphthalene and alkylated naphthalene is increased significantly in oil product.

Description

A kind of method of dual catalyst catalytic pyrolysis waste tire
Technical field
The present invention relates to environmental technology field more particularly to a kind of sides of dual catalyst efficient catalytic thermal cracking waste tire Method.
Background technique
The continuous development of automobile industry can cause very big pollution so that the yield of waste tire is also increasing to environment And the wasting of resources.With gradually increasing for people's environmental consciousness, people increasingly pay attention to the recycling of waste tire, waste and old wheel The pyrolysis technology of tire is the hot issue that current industry is studied.Pyrolytic technique is the organic component of pyrolisis of tires, when When temperature reaches 500 DEG C, it will generate oil, gas and coke, furthermore can also recycle steel wire.Oil can be directly as fuel, can also As the raw material of refinery fuel, high-grade fuel can be also generated by catalyst or as a kind of industrial chemicals.Tire pyrolysis For the gas of generation mainly by C1~C4 hydrocarbon and containing the hydrogen-containing compound of higher heat, these gases contain enough interior can also may be used As fuel, for providing heat needed for thermal decomposition process.Solid carbon by carbon black filler object and rubber pyrolysis charring mistake It is generated in journey.It can be used as a kind of solid fuel, for example carbon black can further refine the active carbon of generation.
In the implementation of the present invention, inventor has found prior art the prior art has at least the following problems: existing waste and old The cracking technology of tire uses high-temperature heating mode, consumes energy larger, needs suitable catalyst degradation thermal cracking temperature.Waste and old wheel Tire will lead to coking by high temperature, and the amount of the product coke or carbon deposit that are formed in pyrolytic process is larger, is unfavorable for its abundant cracking, crack It is insufficient to cause resource utilization not high, it be easy to cause the waste of raw material.It is not strong simultaneously for the selectivity of cracking oil product, it cannot Controllable waste tire is carried out effectively to convert.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of dual catalyst catalytic pyrolysis waste tires Method.It can be effectively reduced waste tire thermal cracking required temperature, effectively reduce coking or carbon deposition phenomenon in pyrolytic process Generation, have apparent selectivity for the generation of aromatic hydrocarbons in cracking oil product, benzene,toluene,xylene, naphthalene and alkylation in oil product The concentration of naphthalene is increased significantly.
A kind of method of dual catalyst catalytic pyrolysis waste tire, which comprises the steps of:
Step 1: waste tire is pre-processed by mechanization, the pretreated 20-60 mesh of waste tire mechanization is obtained Rubber powder, as cracking stock；
Step 2: preparing ZnO-TiO using the addition surfactant cocurrent slurry precipitation method2Catalyst.Detailed process: claim Take 2gTiO2It is dispersed in the beaker equipped with 100mL deionized water, the 0.4gCTAB that addition is dissolved with ethyl alcohol, agitating and heating constant temperature It at 50 DEG C, is sufficiently mixed uniformly, the Na that the zinc nitrate solution and concentration that compound concentration is 1.0mol/L are 1.0mol/L2CO3Solution It is added drop-wise in beaker dropwise respectively simultaneously, carries out precipitation reaction.Precipitating terminates final pH value control 8.0, continues to stir 1h, It standing, at room temperature aging 12h, filters, washing obtains the presoma of catalyst, drying 12h at 110 DEG C, 5h is roasted at 350 DEG C, After cooling, ZnO-TiO is made2Catalyst.
Step 3: the preparation process of modified ZSM-5 zeolite catalyst is as follows: (1) by 10gZSM-5 be put into 200 milliliters it is dense Degree be 0.2mol/L NaOH solution in, then by it in magnetic stirring apparatus 50 DEG C be stirred 4 hours, (2) fast quickly cooling But slurries, are then filtered and thoroughly washing is until solution reaches neutral, then drying 12 hours at 100 DEG C in drying box.(3) The NH for the use of concentration being 1mol/L4NO3Solution carries out ammonia exchange, then uses Muffle furnace calcining sample 4 hours at 550 DEG C.(4) Modified ZSM-5 zeolite is finally leached using NaOH, and hydro-thermal process 4h is carried out at 500 DEG C, the modified ZSM-5 boiling integrated Stone catalyst.
Step 4: according to silica wool → ZSM-5 → quartz → ZnO-TiO in the quartz ampoule of tube furnace2→
Silica wool → raw material → silica wool → ZnO-TiO2→ silica wool → ZSM-5 → silica wool sequence is added.Then Use N2Carrier gas is done, heating cracking waste tire is to 475 DEG C.
The sodium hydroxide solution is formulated by sodium hydroxide and distilled water.
Due to the adoption of the above technical scheme, the present invention has following good effect compared with prior art:
ZnO-TiO2When making catalyst, the influence to gas composition is than more significant, H2Content is substantially reduced and the content of methane Increase, adds ZnO-TiO2H after making catalyst, in gas2S content is remarkably decreased, compared with being not added with catalyst in gas H2S content reduces 87%.Meanwhile ZnO-TiO2Obviously increase pyrolysis gas yield, gas heating value also has increase.
The amount of the product coke or carbon deposit that are formed in pyrolytic process when being not added with catalyst is larger, and after adding catalyst, it is special It is not ZnO-TiO2Mixed catalyst can effectively reduce coking or the generation of carbon deposition phenomenon in pyrolytic process.
And the hydro carbons that the ZSM-5 catalyst being modified generates waste tyre pyrolytic has a significant effect, and finds it to aromatic hydrocarbons Generating especially toluene, dimethylbenzene and benzene has apparent selectivity, because it is with stronger acid and weaker space bit Inhibition effect.It was found that the concentration of mononuclear aromatics obviously increases in oil product.Benzene,toluene,xylene in oil product, naphthalene and alkylated naphthalene it is dense Degree is significantly raised, and the catalytic effect for the ZSM-5 catalyst being modified is obvious, this is related with its surface-active with higher
Detailed description of the invention
Fig. 1 is that structure is added in quartz ampoule dual catalyst and raw material.
Fig. 2 is ZSM-5 Type Zeolites agent Sample Scan electromicroscopic photograph
Fig. 3 is the pretreated 20-60 mesh rubber powder state of aggregation picture of waste tire mechanization；
1:1 quartz ampoule, 2 modified ZSM-5s, 3ZnO-TiO in figure2, 4 reaction raw materials, 5 silica wools.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of method of dual catalyst catalytic pyrolysis waste tire.The preparation method of the present embodiment the following steps are included:
Step 1: waste tire is pre-processed by mechanization, the pretreated 20-60 mesh of waste tire mechanization is obtained Rubber powder, as cracking stock.
Step 2: preparing ZnO-TiO using the addition surfactant cocurrent slurry precipitation method2Catalyst.Detailed process: claim Take 2gTiO2It is dispersed in the beaker equipped with 100mL deionized water, the 0.4gCTAB that addition is dissolved with ethyl alcohol, agitating and heating constant temperature It at 50 DEG C, is sufficiently mixed uniformly, the Na that the zinc nitrate solution and concentration that compound concentration is 1.0mol/L are 1.0mol/L2CO3Solution It is added drop-wise in beaker dropwise respectively simultaneously, carries out precipitation reaction.Precipitating terminates final pH value control 8.0, continues to stir 1h, It standing, at room temperature aging 12h, filters, washing obtains the presoma of catalyst, drying 12h at 110 DEG C, 5h is roasted at 350 DEG C, After cooling, ZnO-TiO is made2Catalyst.
Step 3: the preparation process of modified ZSM-5 zeolite catalyst is as follows: (1) by 10gZSM-5 be put into 200 milliliters it is dense Degree be 0.2mol/L NaOH solution in, then by it in magnetic stirring apparatus 50 DEG C be stirred 4 hours, (2) fast quickly cooling But slurries, are then filtered and thoroughly washing is until solution reaches neutral, then drying 12 hours at 100 DEG C in drying box.(3) Ammonia exchange is carried out using the NH4NO3 solution that concentration is 1mol/L, then uses Muffle furnace calcining sample 4 hours at 550 DEG C.(4) Modified ZSM-5 zeolite is finally leached using NaOH, and hydro-thermal process 4h is carried out at 500 DEG C, the modified ZSM-5 boiling integrated Stone catalyst.
Step 4: according to silica wool → ZSM-5 → silica wool → ZnO-TiO in the quartz ampoule of tube furnace2→ silica wool → raw material → silica wool → ZnO-TiO2→ silica wool → ZSM-5 → silica wool sequence is added.Then carrier gas is done with N2, heated Waste tire is cracked to 475 DEG C.
The method of dual catalyst catalytic pyrolysis waste tire is to 10g waste-tyre rubber-powder used by the present embodiment 1 It is handled, the catalyst amounts are 3g, are purged with N2, use the diamond heating heating-up time for 30min.It was found that with not Catalyst is added to compare, the H2S content in cracked gas is remarkably decreased, significant desulfurization effect, and H2S content reduces by 87%.Meanwhile ZnO-TiO2 makes pyrolysis gas yield reach 26.35%, and gas heating value reaches 28.76MJ/m3.It had been pyrolyzed when being not added with catalyst The amount of the product coke or carbon deposit that are formed in journey is larger, and after adding dual catalyst, coking or carbon distribution in pyrolytic process can be effectively reduced The generation of phenomenon.The influence of hydro carbons, generation especially toluene of the discovery dual catalyst to aromatic hydrocarbons are generated to waste tyre pyrolytic (19.82%), dimethylbenzene (16.91%) and benzene (10.28%) have apparent selectivity.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (1)

1. a kind of method of dual catalyst catalytic pyrolysis waste tire, which is characterized in that comprise the following steps:
(1) waste tire is pre-processed by mechanization, obtains the pretreated 20-60 mesh rubber powder of waste tire mechanization, made For cracking stock；
(2) ZnO-TiO is prepared using the addition surfactant cocurrent slurry precipitation method2Detailed process: catalyst weighs 2g TiO2 Be dispersed in the beaker equipped with 100mL deionized water, the 0.4gCTAB that addition is dissolved with ethyl alcohol, agitating and heating constant temperature at 50 DEG C, It is sufficiently mixed uniformly, the Na that the zinc nitrate solution and concentration that compound concentration is 1.0mol/L are 1.0mol/L2CO3The solution same time-division It not being added drop-wise in beaker dropwise, carries out precipitation reaction, precipitating terminates final pH value control 8.0, continues to stir 1h, stand, Aging 12h at room temperature is filtered, washing, obtains the presoma of catalyst, drying 12h at 110 DEG C, roasts 5h at 350 DEG C, cooling Afterwards, ZnO-TiO is made2Catalyst；
(3) preparation process of modified ZSM-5 zeolite catalyst is as follows: 10gZSM-5, which (a) is put into 200 milliliters of concentration, is In the NaOH solution of 0.2mol/L, then by it in magnetic stirring apparatus 50 DEG C be stirred 4 hours, (b) be quickly cooled down slurry Liquid, is then filtered and thoroughly washing is until solution reaches neutral, then 12 hours dry at 100 DEG C in drying box, (c) use The NH4NO3 solution that concentration is 1mol/L carries out ammonia exchange, then uses Muffle furnace calcining sample 4 hours at 550 DEG C, (d) last Modified ZSM-5 zeolite is leached using NaOH, hydro-thermal process 4h is carried out at 500 DEG C, and the modified ZSM-5 zeolite integrated is urged Agent；
(4) according to silica wool → ZSM-5 → quartz → ZnO-TiO in the quartz ampoule of tube furnace2→ silica wool → raw material → stone English cotton → ZnO-TiO2→ silica wool → ZSM-5 → silica wool sequence is added, and then does carrier gas with N2, and heating cracks waste and old wheel Tire is to 475 DEG C.
CN201910653370.8A 2019-07-19 2019-07-19 A kind of method of dual catalyst catalytic pyrolysis waste tire Pending CN110343539A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114606529A (en) * 2022-02-21 2022-06-10 大全集团有限公司 Method for preparing Zn-SAs/S, N self-doping CM catalyst based on waste tire and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114606529A (en) * 2022-02-21 2022-06-10 大全集团有限公司 Method for preparing Zn-SAs/S, N self-doping CM catalyst based on waste tire and application

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Application publication date: 20191018