CN112295588B - Preparation and application of catalyst for catalytic conversion of pyrolysis oil gas of waste tires - Google Patents
Preparation and application of catalyst for catalytic conversion of pyrolysis oil gas of waste tires Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 65
- 239000010920 waste tyre Substances 0.000 title claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 35
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010419 fine particle Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- 239000003502 gasoline Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002283 diesel fuel Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- -1 ammonium ions Chemical class 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 16
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 50
- 239000000047 product Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 11
- 239000012263 liquid product Substances 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000010327 methods by industry Methods 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 238000011165 process development Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses preparation and application of a catalytic conversion catalyst for pyrolysis of oil gas by waste tires. The technical proposal is as follows: based on the traditional catalyst (NaY type molecular sieve), two rare earth elements La and Ce are introduced to carry out chemical modification to the catalyst, so as to prepare the efficient catalytic pyrolysis catalyst of the fine particles of the waste tires. The fine particles of the waste tires are subjected to pyrolysis in the first-stage reactor and catalytic conversion in the second-stage reactor, the total oil and gas yield reaches more than 61%, and waste tires which are difficult to treat are effectively utilized and converted into high-quality light oil products.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to preparation and application of a catalyst for catalytic conversion of pyrolysis oil gas of waste tires.
Background
Junked tires are common solid wastes in life and have great harm to air and soil, so the junked tires are called as black pollutants. The number of annual tires is 15 hundred million worldwide, china is the large country of the automobile industry, the number of annual tires is up to 4 hundred million, and the number is continuously increasing. The number of discarded tires newly produced each year is also counted for due to vehicle scrapping, tire depreciation, wear and the like. The rubber for preparing the tire mainly comprises synthetic rubber and natural rubber, wherein butadiene rubber and styrene butadiene rubber are particularly used as the main materials in the synthetic rubber. At present, the treatment mode of the junked tires is mainly used as fuel for direct combustion, which causes great waste of organic matter resources and serious environmental pollution. Therefore, the method for efficiently recycling the junked tires is important.
At present, the recycling ways of waste tires reported in the literature mainly comprise direct utilization, tire retreading, regenerated rubber production, vulcanized rubber powder production, heat energy utilization, pyrolysis oil production, gas production and the like. The high-temperature pyrolysis of the tire can generate products such as fuel oil, fuel gas, coke and the like, and the reaction process is efficient and environment-friendly, so that the method is one of the most effective ways for recycling the tire. However, the conventional direct pyrolysis method has low oil and gas production efficiency, poor product quality and poor stability, which greatly limits the application range of the pyrolysis method in the field of waste tire recovery. The catalyst is introduced to assist pyrolysis, so that the reaction efficiency can be improved to a certain extent, and the quality of oil gas obtained by pyrolysis is improved. In addition, the catalytic pyrolysis method has better product selectivity and product stability.
The pore size and si/Al molar ratio of the molecular sieve catalyst determine the activity and selectivity, and the molecular sieve with larger pore size and low molar ratio has high catalytic activity. Shuai Kun et Al (references: shuai Kun, yu, cui Xiaolong, etc.. Waste tire pyrolysis catalysts and process development [ J ]. Programming, 2017,17 (1): 193-200.) have found that molecular sieve catalyst pore size and acidity determine its activity and selectivity, and that si/Al mole ratio is relatively high, and catalytic activity is reduced. The reference has found drawbacks with existing catalysts, but has not found an effective solution. Before the yield of the pyrolysis products of the waste tire particles is stopped, the pyrolysis catalyst is directly contacted with the waste tire particles to cause the occurrence of carbon deposition, so that the catalyst is quickly deactivated and cannot be used for large-scale or continuous production.
Disclosure of Invention
Aiming at the defect of the catalyst performance, the invention prepares the catalytic conversion catalyst for pyrolysis oil gas of waste tires by doping and modifying rare earth elements on the NaY type molecular sieve. Compared with the traditional molecular sieve catalyst, the introduction of rare earth elements reduces pyrolysis energy consumption, improves catalytic pyrolysis reaction efficiency of waste tires, improves oil and gas yields, and improves quality and stability of pyrolysis products. The invention also selects two-stage bed reactors, namely one-stage pyrolysis and two-stage catalytic conversion, avoids mutual interference, is beneficial to the regeneration and utilization of the catalyst, can effectively solve the defects in the prior art, and improves the service efficiency of the catalyst.
The specific technical scheme provided by the invention is as follows:
1. in order to overcome the defects in the prior art, the invention discloses a preparation method of a catalyst for catalytic conversion of pyrolysis oil gas of waste tires, which comprises the following steps:
(1) With saturation (NH) 4 ) 2 SO 4 The solution is used as an exchanger, and is subjected to ammonium exchange with a NaY molecular sieve, and then washed, dried and roasted to obtain NH 4 A Y-type molecular sieve;
(2) In the prepared NH 4 La (OH) with a certain mole ratio is added into the Y molecular sieve 3 、Ce(OH) 4 And roasting for 2-4 hours at 800-1000 ℃ after fully grinding and mixing to obtain the La-containing material 2 O 3 And CeO 2 A Y-type molecular sieve pyrolysis catalyst;
(3) In order to increase the degree of exchange, step (1) may be subjected to a secondary ammonium exchange and calcination until the ammonium ions are no longer increased.
2. As a further preferred aspect, in the step (1), it is characterized in that: during the ammonium exchange, saturated (NH 4 ) 2 SO 4 The aqueous solution is refluxed for 2-3 hours at the temperature of 35-150 ℃.
3. As a further preference, in the step (1), the La-containing powder obtained in the step (2) 2 O 3 And CeO 2 NH in Y-type molecular sieve pyrolysis catalyst 4 The mass ratio of the Y molecular sieve is 95-98%, and the mole ratio of La to Ce is 1: 1-3.
4. As a further preference, the use of the pyrolysis catalyst prepared in step (1) is characterized in that: the prepared pyrolysis catalyst is applied to the catalytic conversion of oil gas after the pyrolysis of fine particles of waste tires, and poor-quality pyrolysis oil gas is further subjected to catalytic cracking modification processing, and the technical process under normal pressure is as follows: fine particles of waste tires with the mass ratio of 0.1-1.5 mm are placed in a first section of fixed bed reactor, a pyrolysis catalyst is placed in a second section of fixed bed reactor, and the mass ratio of solid particles in the first section of reactor to the solid particles in the second section of reactor is 100: and in 0.5-5.0, after air is replaced by nitrogen purging, the reaction temperature of the first section of fixed bed reactor is raised to 430-500 ℃, the reaction temperature of the second section of fixed bed reactor is controlled to be 450-500 ℃, the reaction time of both sections of reactions is controlled to be 1-3 h, so that oil gas obtained after pyrolysis of organic matters in waste tire particles in the first section of fixed bed reactor is converted into light oil gas through catalytic conversion after passing through the second section of fixed bed reactor with a catalyst, and the light oil gas is separated into gas, gasoline, diesel oil and a small part of tar through further condensation cooling.
Advantageous effects
The addition of the rare earth element to the pyrolysis catalyst effectively improves the catalytic pyrolysis reaction efficiency (references: shuai Kun, yu, cui Xiaolong, etc. waste tire pyrolysis catalysts and process development [ J ]. Programming of process engineering, 2017,17 (1): 193-200.). The invention introduces 2 rare earth elements at the same time, and further can lead the inferior heavy oil with heavier raw materials, such as the oil gas heated by coked tar and the oil gas pyrolyzed by waste tires, to be converted into light component oil such as high-quality gasoline, diesel oil and the like through further catalytic pyrolysis of the rare earth catalyst.
The catalyst prepared by the invention can be used for further catalyzing oil gas after pyrolysis of junked tires: more than 2/3 of the liquid product is a high-octane gasoline component with an octane number of 91-93, and less than 1/3 of the liquid product is a diesel component with a cetane number of 35-45. The gas product has a more complex composition than the refinery gas, wherein the non-carbon component accounts for 12.99%, C 1 The components account for 20.65 percent, C 2 The components account for 21.42 percent, C 3 The components account for 24.76 percent, C 4 The components account for 18.42 percent, C 5 The components account for 1.76%, and the total oil and gas yield is 61-65%.
The pyrolysis catalyst reported in the literature is prepared under the alkaline colloid of a Y-type molecular sieve, and is subjected to reaction, precipitation, crystallization, filtration, washing, ammonium exchange, roasting and the like (references: agate Liu Ping, wang Li, lu Yifei, and the like; rare earth modified NaY-type molecular sieve catalytic pyrolysis of waste tires [ J ]. Chemical environmental protection, 2020,40 (2)). The invention adopts ammonium exchange, grinding and mixing, and roasting to prepare the catalyst, so that the preparation process of the catalyst is simplified, the cost is saved, and the quality of the catalyst is improved.
Compared with the reference (reference: mushroom Liu Ping, wang Li, lu Yifei, and the like) that the rare earth modified NaY molecular sieve catalyzes and pyrolyzes the waste tire [ J ]. Chemical industry environmental protection, 2020,40 (2)), the two-stage bed reaction process provided by the invention can avoid the direct contact of the waste tire material and the catalyst, and reduce the occurrence of carbon deposition phenomenon. According to the technical method of the reference, the waste tire particles and the catalyst are mixed together for heating reaction, after the pyrolysis reaction is completed, unreacted solid particles in the waste tire and new coke produced by pyrolysis can be covered on the surface of the catalyst to occupy the active site of the catalyst, so that the activity of the catalyst is greatly reduced, and the catalyst can only be used once. The process method effectively avoids the rapid deactivation of the catalyst, the catalyst can be continuously used for a long time, and the catalyst can be continuously used after being regenerated when the activity is reduced to 75% of the initial activity. Therefore, the two-stage fixed bed process, the one-stage pyrolysis and the two-stage catalytic conversion process can effectively solve the defects in the prior art and improve the service efficiency of the catalyst.
Compared with the prior art (references: mushroom Liu Ping, wang Li, lu Yifei, and the like), the catalyst prepared by the invention has the advantages that the rare earth modified NaY type molecular sieve is used for catalytic pyrolysis of waste tires [ J ]. Chemical industry is environment-friendly, 2020,40 (2)), and the quality of liquid products is greatly improved. The fuel obtained by the reference can only be used for occasions of direct combustion of boilers, thermal power plants and the like, and cannot be used as vehicle fuel oil, and the produced fuel oil can not meet the requirements of transportation oil although the problem of partial conversion of waste tires is effectively solved. Most of liquid products in the process are high-grade gasoline components with the octane number of 91-93, and the liquid products are diesel components with the cetane number of 35-45.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited by the examples.
Example 1 preparation of catalyst
In order to further improve the oil gas yield of catalytic pyrolysis of junked tires and the quality of products thereof, two rare earth elements are creatively introduced into a Y-type molecular sieve at the same time, and a preparation method of a pyrolysis catalyst is provided:
(1) Adopts NaY molecular sieve as carrier, uses saturated (NH) 4 ) 2 SO 4 The solution is used as an exchanger, the two raw materials are refluxed for 3 hours at the temperature of 150 ℃ for carrying out ammonium exchange, and then washed, dried and roasted to obtain NH 4 The Y-type molecular sieve can be subjected to secondary ammonium exchange and roasting for improving the exchange degree until ammonium ions are not increased any more;
(2) Taking the NH prepared by the steps 4 100g of Y molecular sieve, to which 5g of a catalyst having a molar ratio of 1:2 La (OH) 3 And Ce (OH) 4 Fully grinding and mixing, and roasting at 880 ℃ for 3 hours to obtain the La-containing material 2 O 3 And CeO 2 A Y-type molecular sieve pyrolysis catalyst.
Example 2 catalytic pyrolysis of oil gas after pyrolysis of junked tires
La-containing articles prepared by the present invention 2 O 3 And CeO 2 The catalyst is used for catalyzing and pyrolyzing oil gas obtained by pyrolyzing waste tires. Before the experiment, weighing 100g of waste tire materials with granularity of 0.2mm by an electronic scale, and putting the waste tire materials into a first section of fixed bed reactor; weighing La-containing 2 O 3 And CeO 2 0.5g of the Y-type molecular sieve pyrolysis catalyst is added into the second-stage fixed bed reactor. The second section of fixed bed reactor is positioned above the first section of fixed bed reactor, the two sections of reactors are connected by a pipeline and a valve, the outlet of the second section of reactor is connected with a fractionating tower and a cooling and separating device, and the products of catalytic pyrolysis are separated into noncondensable gas, gasoline, diesel oil and base oil; before the experiment, nitrogen with the concentration of 0.60L/min is used for purging for 30min, then the reaction temperature of the first-stage fixed bed reactor is raised to 500 ℃, the reaction temperature of the second-stage fixed bed reactor is controlled to be 500 ℃, the reaction time of both stages is controlled to be 3h, so that the oil vapor generated after the pyrolysis of the organic matters in the waste tire particles in the first-stage fixed bed reactor passes through the fixed bed reactor with the catalyst in the second stage, is catalytically converted into light oil vapor, and is further condensed and cooled, separated into gas, gasoline, diesel oil and a small part of tar, and the pyrolysis-catalytic conversion of the waste tire particles in the two stages is realizedAnd (5) recording the test, and calculating the oil gas yield.
Example 3 catalytic pyrolysis of oil gas after pyrolysis of junked tires
La-containing articles prepared by the present invention 2 O 3 And CeO 2 The catalyst is used for catalyzing and pyrolyzing oil gas obtained by pyrolyzing waste tires. Before the experiment, weighing 100g of waste tire materials with granularity of 0.2mm by an electronic scale, and putting the waste tire materials into a first section of fixed bed reactor; weighing La-containing 2 O 3 And CeO 2 1.5g of the Y-type molecular sieve pyrolysis catalyst is added into the second-stage fixed bed reactor. The second section of fixed bed reactor is positioned above the first section of fixed bed reactor, the two sections of reactors are connected by a pipeline and a valve, the outlet of the second section of reactor is connected with a fractionating tower and a cooling and separating device, and the products of catalytic pyrolysis are separated into noncondensable gas, gasoline, diesel oil and base oil; before the experiment, nitrogen with the concentration of 0.60L/min is used for purging for 30min, then the reaction temperature of the first section of fixed bed reactor is raised to 500 ℃, the reaction temperature of the second section of fixed bed reactor is controlled to be 500 ℃, the reaction time of both sections of reactions is controlled to be 3h, the oil vapor after pyrolysis of organic matters in waste tire particles in the first section of fixed bed reactor is converted into light oil vapor through catalytic conversion after passing through the second section of fixed bed reactor with the catalyst, and the light oil vapor is separated into gas, gasoline, diesel oil and a small part of tar through further condensation and cooling, the pyrolysis-catalytic conversion experiment of the waste tire particles of the two sections of fixed beds is recorded, and the oil vapor yield is calculated.
Example 4 catalytic pyrolysis of junked tires
La-containing articles prepared by the present invention 2 O 3 And CeO 2 The catalyst is used for catalyzing and pyrolyzing oil gas obtained by pyrolyzing waste tires. Before the experiment, weighing 100g of waste tire materials with granularity of 0.2mm by an electronic scale, and putting the waste tire materials into a first section of fixed bed reactor; weighing La-containing 2 O 3 And CeO 2 2.5g of the Y-type molecular sieve pyrolysis catalyst is added into the second-stage fixed bed reactor. The second section of fixed bed reactor is positioned above the first section of fixed bed reactor, the two sections of reactors are connected by a pipeline and a valve, the outlet of the second section of reactor is connected with a fractionating tower and a cooling separation device,separating the catalytic cracking product into noncondensable gas, gasoline, diesel oil and base oil; before the experiment, nitrogen with the concentration of 0.60L/min is used for purging for 30min, then the reaction temperature of the first section of fixed bed reactor is raised to 500 ℃, the reaction temperature of the second section of fixed bed reactor is controlled to be 500 ℃, the reaction time of both sections of reactions is controlled to be 3h, the oil vapor after pyrolysis of organic matters in waste tire particles in the first section of fixed bed reactor is converted into light oil vapor through catalytic conversion after passing through the second section of fixed bed reactor with the catalyst, and the light oil vapor is separated into gas, gasoline, diesel oil and a small part of tar through further condensation and cooling, the pyrolysis-catalytic conversion experiment of the waste tire particles of the two sections of fixed beds is recorded, and the oil vapor yield is calculated.
Example 5 catalytic pyrolysis of junked tires
La-containing articles prepared by the present invention 2 O 3 And CeO 2 The catalyst is used for catalyzing and pyrolyzing oil gas obtained by pyrolyzing waste tires. Before the experiment, weighing 100g of waste tire materials with granularity of 0.2mm by an electronic scale, and putting the waste tire materials into a first section of fixed bed reactor; weighing La-containing 2 O 3 And CeO 2 5.0g of the Y-type molecular sieve pyrolysis catalyst is added into the second-stage fixed bed reactor. The second section of fixed bed reactor is positioned above the first section of fixed bed reactor, the two sections of reactors are connected by a pipeline and a valve, the outlet of the second section of reactor is connected with a fractionating tower and a cooling and separating device, and the products of catalytic pyrolysis are separated into noncondensable gas, gasoline, diesel oil and base oil; before the experiment, nitrogen with the concentration of 0.60L/min is used for purging for 30min, then the reaction temperature of the first section of fixed bed reactor is raised to 500 ℃, the reaction temperature of the second section of fixed bed reactor is controlled to be 500 ℃, the reaction time of both sections of reactions is controlled to be 3h, the oil vapor after pyrolysis of organic matters in waste tire particles in the first section of fixed bed reactor is converted into light oil vapor through catalytic conversion after passing through the second section of fixed bed reactor with the catalyst, and the light oil vapor is separated into gas, gasoline, diesel oil and a small part of tar through further condensation and cooling, the pyrolysis-catalytic conversion experiment of the waste tire particles of the two sections of fixed beds is recorded, and the oil vapor yield is calculated.
Pyrolysis catalyst catalyzes the total yield of pyrolysis product oil gas
| Numbering device | Size of the device | Catalyst amount/g | Total oil and gas yield% |
| LT0.2-Ⅳa | 0.2mm | 0.5 | 61.2 |
| LT0.2-Ⅳb | 0.2mm | 1.5 | 62.3 |
| LT0.2-Ⅳc | 0.2mm | 2.5 | 63.5 |
| LT0.2-Ⅳd | 0.2mm | 5.0 | 64.3 |
Compared with the traditional molecular sieve catalyst, the pyrolysis catalyst added with the rare earth element can obviously reduce the initial temperature and the termination temperature of the catalytic pyrolysis process of the waste tires, and effectively improve the catalytic pyrolysis reaction efficiency (references: shuai Kun, yu, cui Xiaolong, and the like; waste tire pyrolysis catalyst and process research progress [ J)]Process engineering report 2017,17 (1): 193-200.). The invention introduces 2 rare earth elements at the same time, and further can lead the inferior heavy oil with heavier raw materials, such as the oil gas heated by coked tar and the oil gas pyrolyzed by waste tires, to be converted into light component oil such as high-quality gasoline, diesel oil and the like through further catalytic pyrolysis of the rare earth catalyst. The further catalytic result of the catalyst prepared by the invention on the oil gas after pyrolysis of the waste tires is that more than 2/3 of the liquid product is a high-octane gasoline component with the octane number of 91-93, and less than 1/3 of the liquid product is a diesel component with the cetane number of 35-45. While the composition of the gaseous product is more complex than that of the refinery gas, wherein C 0 The components account for 12.99 percent, C 1 The components account for 20.65%，C 2 The components account for 21.42 percent, C 3 The components account for 24.76 percent, C 4 The components account for 18.42 percent, C 5+ The composition accounts for 1.76%, the pyrolysis catalyst reported in the literature with the total oil and gas yield of 61-65% is prepared under the alkaline colloid of a Y-type molecular sieve, and the pyrolysis catalyst is prepared through the steps of reaction, precipitation, crystallization, filtration, washing, ammonium exchange, roasting and the like (references: agaric Liu Ping, wang Li, lu Yifei, and the like; rare earth modified NaY-type molecular sieve catalytic pyrolysis of waste tires [ J)]Chemical environmental protection, 2020,40 (2)). The invention adopts ammonium exchange, grinding and mixing, and roasting to prepare the catalyst, thus simplifying the preparation process of the catalyst. The two-stage bed reaction process provided by the invention can avoid direct contact between the waste tire material and the catalyst, and reduces the occurrence of carbon deposition phenomenon and reference documents: agate Liu Ping, wang Li, lu Yifei, etc. rare earth modified NaY molecular sieve catalytic pyrolysis of scrap tires [ J]Compared with the chemical environment-friendly and 2020,40 (2) process method, the waste tire particles and the catalyst are mixed together for heating reaction, after the pyrolysis reaction is completed, unreacted solid particles in the waste tire and new coke produced by pyrolysis can be covered on the surface of the catalyst to occupy the active site of the catalyst, so that the activity of the catalyst is greatly reduced and the catalyst can only be used once. The process method effectively avoids the rapid deactivation of the catalyst, the catalyst can be continuously used for a long time, and the catalyst can be continuously used after being regenerated when the activity is reduced to 75% of the initial activity. Therefore, the two-stage fixed bed process, the one-stage pyrolysis and the two-stage catalytic conversion process can effectively solve the defects in the prior art and improve the service efficiency of the catalyst. The further catalytic conversion result of the catalyst prepared by the invention to the oil vapor after pyrolysis of the waste tires is compared with the prior art (references: mushroom Liu Ping, wang Li, lu Yifei, etc.. Rare earth modified NaY molecular sieve catalytic pyrolysis of waste tires [ J]Compared with chemical engineering environment protection, 2020,40 (2)), the quality of the liquid product is greatly improved. The fuel obtained by the reference can only be used for occasions of direct combustion of boilers, thermal power plants and the like, and cannot be used as vehicle fuel oil, and the produced fuel oil can not meet the requirements of transportation oil although the problem of partial conversion of waste tires is effectively solved. The process is largePart of the liquid product is a high-grade gasoline component with an octane number of 91-93, and the other part of the liquid product is a diesel component with a cetane number of 35-45.
Although embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations may be made to these embodiments without departing from the principles of the present invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. The preparation of the catalyst for catalytic conversion of pyrolysis oil gas of waste tires is characterized by comprising the following steps:
1) With saturation (NH) 4 ) 2 SO 4 The solution is used as an exchanger to carry out ammonium exchange with NaY molecular sieve: the two raw materials are refluxed for 2 to 3 hours at the temperature of 35 to 150 ℃ for ammonium exchange, and then washed, dried and roasted to obtain NH 4 A Y-type molecular sieve; the ammonium exchange is carried out, and secondary ammonium exchange and roasting are carried out for improving the exchange degree until ammonium ions are not increased any more;
2) Taking the NH prepared by the steps 4 100g of Y molecular sieve, to which 5g of a molar ratio 1:2 La (OH) 3 And Ce (OH) 4 Fully grinding and mixing, and roasting at 880 ℃ for 2-4 hours to obtain the La-containing material 2 O 3 And CeO 2 A Y-type molecular sieve pyrolysis catalyst.
2. La-containing prepared according to claim 1 2 O 3 And CeO 2 The application of the Y-type molecular sieve pyrolysis catalyst is characterized in that:
the prepared pyrolysis catalyst is applied to the catalytic conversion of oil gas after the pyrolysis of fine particles of waste tires, and poor-quality pyrolysis oil gas is further subjected to catalytic cracking modification processing, and the technical process under normal pressure is as follows: the method comprises the steps of placing fine particles of waste tires with the diameter of 0.1-1.5 mm into a first section fixed bed reactor, placing a pyrolysis catalyst into a second section fixed bed reactor, wherein the mass ratio of solid particles in the first section reactor to solid particles in the second section reactor is 100:0.5-5.0, after air is replaced by nitrogen purging, heating the first section fixed bed reactor to 430-500 ℃, controlling the reaction temperature of the second section fixed bed reactor to 450-500 ℃, controlling the reaction time of both sections to 1-3 h, and enabling oil gas after pyrolysis of organic matters in the waste tire particles in the first section fixed bed reactor to pass through the second section fixed bed reactor filled with the catalyst, then, carrying out catalytic conversion into light oil gas, and further condensing and cooling, and separating the light oil gas, gasoline, diesel oil and a small part of tar.
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