CN108329514B - Method for processing waste plastics and cellulose - Google Patents
Method for processing waste plastics and cellulose Download PDFInfo
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- CN108329514B CN108329514B CN201810142826.XA CN201810142826A CN108329514B CN 108329514 B CN108329514 B CN 108329514B CN 201810142826 A CN201810142826 A CN 201810142826A CN 108329514 B CN108329514 B CN 108329514B
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- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention discloses a method for processing waste plastics and cellulose. The method comprises the following steps: the method comprises the steps of obtaining a product obtained by catalytically cracking waste plastics through an iron naphthenate and/or molybdenum naphthenate and HY molecular sieve catalyst, separating to obtain a liquid product I, a gas I and an insoluble substance I, obtaining a mixed solvent containing a liquid product II and a residual liquid product III through the liquid product I and a cyclohexane mixed solvent, carrying out catalytic reaction on the liquid product I and the cellulose, obtaining a liquid product I, a gas I and an insoluble substance I through separation, obtaining a liquid product II, a liquid product III and a residual liquid product iv through the liquid product I and the cyclohexane extraction respectively, carrying out deep catalytic cracking reaction on the liquid product III, the liquid product iv, the insoluble substance I and the insoluble substance I, carrying out gas-liquid separation on the obtained product, and obtaining a liquid product VI and a liquid product VII through the liquid product V through the separation and the tetrahydrofuran and the cyclohexane extraction separation respectively. The method not only improves the overall conversion rate, but also promotes the target reaction so as to improve the liquid yield.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for processing waste plastics and cellulose.
Background
The garbage generated by using a large amount of plastic products not only seriously pollutes the environment, but also causes the waste of resources. At present, plastic products are huge in consumption amount, and a large amount of waste plastics are generated every year, but at present, the recycling, collecting and sorting efficiency of the waste plastics is generally low, and various types of waste plastics are difficult to supply continuously, so that the single treatment of the waste plastics is difficult to form large-scale continuous production. Although the yield of the cellulose is large, at present, most of the cellulose is directly incinerated, which causes a great amount of air pollution and waste of resources. At present, the liquefaction technology of plastics and the optimized utilization of cellulose have been studied, and if waste plastics are added into the cellulose for co-pyrolysis treatment, the advantages of the pyrolysis of the two can be utilized, so that the yield of valuable products of the two is higher. However, direct liquefaction research on plastics and cellulose respectively finds that the difference between reaction conditions required by the plastics and the cellulose and process conditions such as a catalyst is large, direct liquefaction of the waste plastics and the cellulose has high requirements on the types of reactants, the reaction conditions, the catalyst and the like, and certain challenges are brought to joint treatment of the waste plastics and the cellulose.
disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for processing waste plastics and cellulose. Compared with the existing treatment process of waste plastics and cellulose, the method not only improves the overall conversion rate, but also promotes the target reaction, thereby improving the liquid yield and improving the economic benefit and the environmental benefit of the whole process.
The invention provides a method for processing waste plastics and cellulose, which comprises the following steps:
(1) Waste plastics are added into a catalytic reactor A, catalytic cracking reaction is carried out under the action of a catalyst 1, and the obtained cracking product is separated to obtain a liquid product I, a gas I and insoluble substances I;
(2) Cooling the liquid product I obtained in the step (1), and introducing a tetrahydrofuran and cyclohexane mixed solvent for extraction to respectively obtain a tetrahydrofuran and cyclohexane mixed solvent containing a liquid product II and a residual liquid product III;
(3) adding cellulose, the tetrahydrofuran solution containing the liquid product II obtained in the step (2) and a cyclohexane mixed solvent into a catalytic reactor B for catalytic reaction, and separating to obtain a liquid product i, a gas i and an insoluble substance i;
(4) Cooling the liquid product i obtained in the step (3), sequentially introducing tetrahydrofuran and a cyclohexane solvent for extraction to respectively obtain a tetrahydrofuran solution containing the liquid product ii, a cyclohexane solution containing the liquid product iii and a residual liquid product iv, and removing the solvent through distillation treatment to obtain a liquid product ii and a liquid product iii;
(5) adding the residual liquid product III and the residual liquid product iv obtained in the step (2) and the step (4) and the insoluble substance I and the insoluble substance I obtained in the step (1) and the step (3) into a catalytic reactor C, carrying out deep catalytic cracking reaction under the action of a catalyst 2, and separating the obtained cracking product to obtain a liquid product V, a gas V and an insoluble substance V;
(6) Cooling the liquid product V obtained in the step (5), sequentially introducing tetrahydrofuran and cyclohexane solvent for extraction to respectively obtain a tetrahydrofuran solution containing a liquid product VI, a cyclohexane solution containing a liquid product VII and a residual liquid product VIII, and removing the solvent through distillation treatment to obtain a liquid product VI and a liquid product VII;
wherein, the catalyst 1 in the step (1) consists of two catalysts, one is iron naphthenate and/or molybdenum naphthenate, and the other is HY molecular sieve catalyst.
In the present invention, the catalytic reactors A, B and C are both slurry bed catalytic cracking reactors.
In the invention, the waste plastics in the step (1) mainly comprise one or a mixture of more of polyethylene Plastics (PE), Polypropylene Plastics (PP) and Polystyrene (PS), and the total content of the waste plastics is not less than 80 percent of the total mass of the added waste plastics.
in the invention, the mass ratio of the iron naphthenate and/or molybdenum naphthenate to the HY molecular sieve catalyst in the catalyst 1 in the step (1) is 0.1-0.5:1, preferably 0.1-0.3: 1.
in the invention, the catalyst 1 in the step (1) is used in an amount of 5-20%, preferably 10-15% of the total mass of the added waste plastics.
in the present invention, the reaction conditions of the catalytic cracking reaction in step (1) are as follows: the reaction temperature is 350-550 ℃, and preferably 400-480 ℃; the reaction time is 30 to 150 minutes, preferably 45 to 120 minutes; the reaction is carried out under stirring, and the stirring speed is 350-600 r/min, preferably 400-500 r/min; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 2-4MPa, preferably 2.5-3.5 MPa.
In the invention, the mass ratio of the mixed solvent of tetrahydrofuran and cyclohexane in the step (2) to the liquid product I is 1-3:1, wherein the mass ratio of tetrahydrofuran to cyclohexane is 1-3:1, and preferably 1-2: 1.
In the present invention, the cooling in step (2), step (4) and step (6) is preferably to cool the liquid product I, the liquid product cold I and the liquid product V to room temperature.
In the present invention, the distillation treatment in the steps (4) and (6) is a distillation method which is conventional in the art to remove tetrahydrofuran or cyclohexane solvent.
In the invention, the cellulose in the step (3) is one or more of plant fiber substances such as straws, barks, straws and the like.
In the present invention, the cellulose in step (3) is preferably subjected to a pretreatment such as at least one of pulverization and dehydration treatment before being fed to the catalytic reactor B. Wherein said pulverization, the powder obtained by the pulverization, has a length of preferably not more than 20 mm. The dehydration treatment is carried out under the anaerobic condition, the treatment temperature is 100-200 ℃, and the treatment time is 60-120 minutes.
In the invention, the tetrahydrofuran solution containing the liquid product II obtained in the step (2) and a cyclohexane mixed solvent are added in the step (3), and the mass ratio of the cellulose to the tetrahydrofuran solution containing the liquid product II and the cyclohexane mixed solvent is 0.8-1.2: 1.
in the invention, a certain amount of iron naphthenate and/or molybdenum naphthenate can be added in the step (3) according to the requirement, so that the total mass content of iron and molybdenum in the catalytic reactor B is 800-1200 ppm. Adding a sulfur source with the mass content of 4000-: 1, wherein the selected sulfur source is one or more of sulfur, hydrogen sulfide, carbon disulfide and the like.
In the present invention, the reaction conditions of the catalytic reaction in step (3) are as follows: the reaction temperature is 400-600 ℃, preferably 450-550 ℃; the reaction time is 30 to 100 minutes, preferably 60 to 100 minutes; the reaction is carried out under stirring, and the stirring speed is 350-600 r/min, preferably 400-500 r/min; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 4-8MPa, preferably 5-6.5 MPa. Further, preferred reaction conditions are as follows: the reaction temperature of the catalytic reaction in the step (3) is at least 50 ℃ higher than that of the catalytic reaction in the step (1), and the hydrogen partial pressure of the catalytic reaction in the step (3) is at least 2MPa higher than that of the catalytic reaction in the step (1).
In the invention, the catalyst 2 in the step (5) is an HZSM-5 and HY composite molecular sieve catalyst, and the mass ratio of HZSM-5 to HY is 0.5-2:1, preferably a phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst, wherein the mass content of phosphorus is 1.5-7.0%, and the mass content of tungsten is 0.3-2.0%. The using amount of the catalyst 2 is 5-20%, preferably 10-15% of the total mass of all the added reaction materials added into the catalytic reactor C in the step (5).
in the present invention, the preparation method of the catalyst 2 used is preferably as follows: mixing HZSM-5 and HY to obtain a composite molecular sieve, impregnating the composite molecular sieve with a phosphoric acid solution with the mass concentration of 10-20%, and drying at 80-110 ℃ for 1-3 hours; and (2) impregnating the composite molecular sieve again with a sodium tungstate aqueous solution with the mass concentration of 1-2%, drying at 80-110 ℃ for 5-10 hours, and finally roasting at 330-380 ℃ for 4-7 hours to obtain the catalyst 2 after molding.
In the invention, the catalyst 2 can be formed by a conventional method, such as tabletting and the like, and a forming auxiliary agent can be added in the forming process according to the requirement. After tableting, sieving is performed as necessary, and solid particles having a particle size of 30 to 70 mesh, preferably 40 to 60 mesh, are taken as the catalyst 2. The phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst is prepared by using one or more of phosphotungstic acid, phosphorus oxide, phosphotungstate, phosphoric acid, phosphate and the like as possible phosphorus, and one or more of phosphotungstic acid, tungsten oxide, phosphotungstate and the like as possible tungsten.
In the invention, the reaction conditions of the deep catalytic cracking reaction in the step (5) are as follows: the reaction temperature is 400-700 ℃, preferably 500-600 ℃; the reaction time is 60-150 minutes; the reaction is carried out under stirring, and the stirring speed is 350-600 revolutions per minute; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 5-10 MPa. Further, preferred reaction conditions are as follows: the reaction temperature of the catalytic reaction in the step (5) is at least 50 ℃ higher than that of the catalytic reaction in the step (3), and the hydrogen partial pressure of the catalytic reaction in the step (5) is at least 1MPa higher than that of the catalytic reaction in the step (3).
Compared with the prior art, the invention has the following advantages:
The invention combines the treatment of cellulose and the catalytic cracking of waste plastics, and changes waste into valuable. The invention fully utilizes the characteristics of the two reactions, optimizes the reaction conditions respectively, and improves the overall conversion rate and promotes the target reaction compared with the conventional co-treatment of waste plastics and cellulose, thereby improving the yield of cyclohexane soluble substances and tetrahydrofuran soluble substances and reducing the insoluble substance amount. Particularly, the waste plastic catalytic cracking uses iron naphthenate and/or molybdenum naphthenate and HY molecular sieves as catalysts, and then liquid products obtained by tetrahydrofuran extraction and cellulose are pyrolyzed together, so that the dissolution of polar products in the catalytic reaction process of the cellulose is improved, the conversion rate of the cellulose is improved, and the cost is saved. In addition, the invention collects and mixes the insoluble substances after the catalytic reaction of the waste plastics and the cellulose, and adds the residual liquid product which is not extracted by tetrahydrofuran and cyclohexane after the catalytic reaction of the waste plastics and the cellulose to carry out deep catalytic cracking reaction under the action of the catalyst, thereby reducing the generation of a large amount of waste residues. For waste residues which are difficult to treat, particularly the phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst, the cracking temperature is mild, and the cracking rate is high.
In addition, the method has the advantages of simple process flow, mild reaction conditions, simplicity, feasibility and low cost, solves the problems of difficult treatment and low recycling value of a large amount of waste plastics and cellulose, relieves the environmental pressure caused by the large amount of waste plastics and cellulose, changes waste into valuable, and obviously improves the added value of the waste plastics and the cellulose.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
The reference numerals are explained below: 1. a catalytic reactor A; 2. a gas-liquid-solid separator a; 3. an extraction device a which takes tetrahydrofuran and cyclohexane as solvents is sequentially arranged; 4. a catalytic reactor B; 5. a gas-liquid-solid separation device b; 6. an extraction device b which takes tetrahydrofuran and cyclohexane as solvents is sequentially arranged; 7. a catalytic reactor C; 8. a gas-solid separation device c; 9. an extraction device c which takes tetrahydrofuran and cyclohexane as solvents is sequentially arranged; 21. a liquid product I; 22. a gas I; 23 insoluble I; 31. a mixed solvent of tetrahydrofuran and cyclohexane containing the liquid product II; 32. the remaining liquid product III; 51. a liquid product i; 52. a gas i; 53. insoluble substances i; 61. a liquid product ii; 62. liquid product iii; 63. the remaining liquid product iv; 81. a liquid product V; 82. a gas V; 83. insoluble substances V; 91. a liquid product VI; 92. a liquid product VII; 93. the remaining liquid product VIII.
Detailed Description
The method of processing waste plastic and cellulose of the present invention will be further described below with reference to specific examples, but the scope of the present invention is not limited thereto. In the present invention, wt% represents a mass fraction.
As shown in fig. 1, the present invention provides a method of processing waste plastic and cellulose, comprising the steps of:
(1) Waste plastics are added into a catalytic reactor A1, catalytic cracking reaction is carried out under the action of a catalyst 1, and the obtained cracking product is subjected to a gas-liquid-solid separator a 2 to obtain a liquid product I21, a gas I22 and insoluble substances I23;
(2) Cooling the liquid product I21 obtained in the step (1), and introducing the cooled liquid product I into an extraction device a 3 using a mixed solvent of tetrahydrofuran and cyclohexane as a solvent for extraction to respectively obtain a mixed solvent 31 of tetrahydrofuran and cyclohexane containing a liquid product II and a residual liquid product III 32;
(3) Adding cellulose into a catalytic reactor B4 for dehydration, then adding the tetrahydrofuran and cyclohexane mixed solvent 31 containing the liquid product II obtained in the step (2), adding a sulfur source for catalytic reaction, and separating by a gas-liquid-solid separator B5 to obtain a liquid product i 51, a gas i 52 and an insoluble substance i 53;
(4) Cooling the liquid product i 51 obtained in the step (3), sequentially introducing the cooled liquid product into an extraction device b 6 with tetrahydrofuran and cyclohexane as solvents for extraction to respectively obtain a tetrahydrofuran solution containing the liquid product ii, a cyclohexane solution containing the liquid product iii and a residual liquid product iv 63, and removing the solvents by distillation treatment to obtain a liquid product ii 61 and a liquid product iii 62;
(5) Adding the residual liquid product III 32 and the residual liquid product iv 63 obtained in the step (2) and the step (4) and the insoluble substances I23 and the insoluble substances I53 obtained in the step (1) and the step (3) into a catalytic reactor C7, carrying out deep catalytic cracking reaction under the action of a catalyst 2, and separating the obtained cracked product by a gas-liquid-solid separation device C8 to obtain a liquid product V81, a gas V82 and an insoluble substance V83;
(6) And (3) cooling the liquid product V81 obtained in the step (5), introducing the cooled liquid product V81 into an extraction device c 9 which is sequentially provided with tetrahydrofuran and cyclohexane as solvents for extraction to respectively obtain a tetrahydrofuran solution containing a liquid product VI, a cyclohexane solution containing a liquid product VII and the residual liquid product VIII93, and removing the solvents by distillation treatment to obtain a liquid product VI 91 and a liquid product VII 92.
Wherein, the insoluble substances V83 are waste residues which do not participate in the reaction any more, and the residual liquid product VIII93 can be recycled to the catalytic reactor C7 for further catalytic cracking reaction.
Wherein the products in Table 1 are gas, cyclohexane soluble, tetrahydrofuran soluble and waste residue, wherein the gas is gas I22, gas I52 and gas V82, the cyclohexane soluble is liquid product iii 62 and liquid product VII 92, the tetrahydrofuran soluble is liquid product ii 61 and liquid product VI 91, and the residue is insoluble V83 and residual liquid product VIII 93. The conversion rate is the percentage of the total mass of gas, cyclohexane soluble matter and tetrahydrofuran soluble matter in the product to the mass of four products. In the present invention, the gas is mainly a low-carbon olefin having four or less carbon atoms such as ethylene and propylene.
Catalyst 1-A used in the examples of the present invention: the catalyst consists of two catalysts, one is iron naphthenate and molybdenum naphthenate, and the other is HY molecular sieve catalyst. According to the weight, the mass ratio of the iron naphthenate to the molybdenum naphthenate to the HY molecular sieve catalyst is 0.15:1, and the mass ratio of the iron naphthenate to the molybdenum naphthenate is 1: 1.
Catalysts 1-B used in the examples of the present invention: the catalyst consists of two catalysts, one is iron naphthenate, and the other is HY molecular sieve catalyst. The mass ratio of the iron naphthenate to the HY molecular sieve catalyst is 0.18:1 by weight.
Catalysts 1-C used in the examples of the present invention: the catalyst consists of two kinds of catalyst, one is molybdenum naphthenate and the other is HY molecular sieve catalyst. The mass ratio of the molybdenum naphthenate to the HY molecular sieve catalyst is 0.12: 1.
The phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst CAT-A used in the embodiment of the invention is specifically as follows: the mass ratio of the HZSM-5 to the HY composite molecular sieve is 1:1, the mass content of phosphorus is 3 percent, the mass content of tungsten is 1.2 percent, and the preparation method comprises the following steps: mixing HZSM-5 with HY molecular sieve, impregnating the composite molecular sieve with 15% phosphoric acid solution, and drying at 100 deg.C for 2 hr; soaking the composite molecular sieve in 1.5% sodium tungstate water solution, drying at 100 deg.c for 8 hr, final roasting at 350 deg.c for 6 hr, tabletting to form, sieving and taking solid particle of 40-60 mesh size as the P and W modified HZSM-5 and HY composite molecular sieve catalyst CAT-A.
The HZSM-5 and HY composite molecular sieve catalyst CAT-B used in the embodiment of the invention is specifically as follows: the mass ratio of the HZSM-5 to the HY composite molecular sieve is 1:1, the preparation method comprises the following steps: mixing HZSM-5 and HY composite molecular sieve, drying at 100 deg.C for 8 hr, calcining at 350 deg.C for 6 hr, tabletting, molding, and sieving to obtain solid particles of 40-60 meshes as catalyst CAT-B of HZSM-5 and HY composite molecular sieve.
example 1
Selecting 2g of a mixture of three plastics of 50 wt% of HDPE, 30 wt% of PET and 20 wt% of PS as a raw material for waste plastic reaction, adding the raw material into a slurry bed catalytic cracking reactor A, and carrying out catalytic cracking reaction under the catalytic action of a catalyst 1-A, wherein the addition amount of the catalyst 1-A is 12% of the total mass of the waste plastic, and the reaction conditions of the catalytic cracking reaction are as follows: the reaction temperature is 435 ℃, the reaction time is 80 minutes, the stirring speed is 440 revolutions per minute, hydrogen needs to be introduced into the catalytic reactor A in the reaction, the hydrogen partial pressure is 2.8MPa, and the products after the reaction are separated to obtain a liquid product I, a gas I and an insoluble substance I; cooling the liquid product I to room temperature, and then introducing a tetrahydrofuran and cyclohexane mixed solvent for extraction, wherein the mass ratio of the tetrahydrofuran and cyclohexane mixed solvent to the liquid product I is 1.5:1, the mass ratio of the tetrahydrofuran to the cyclohexane is 2:1, and respectively obtaining the tetrahydrofuran and cyclohexane mixed solvent containing the liquid product II and the residual liquid product III; crushing 3g of straws into powder with the length of about 10mm, dehydrating the powder under the anaerobic condition, wherein the treatment temperature is 130 ℃, the treatment time is 70 minutes, the pretreated straws are added into a slurry bed catalytic cracking reactor B, a tetrahydrofuran and cyclohexane mixed solvent containing a liquid product II is introduced into the slurry bed catalytic cracking reactor B, then ferric naphthenate and molybdenum naphthenate are added into the slurry bed catalytic cracking reactor B, so that the slurry bed catalytic cracking reactor B contains 500ppm of ferric naphthenate and molybdenum naphthenate catalysts, and sulfur with the mass content of 6000ppm is added as a vulcanizing agent, so that the mass ratio of the sulfur content to the total content of iron and molybdenum in the catalytic reactor B is 6: 1, then carrying out the reaction under the following reaction conditions: the reaction temperature is 515 ℃, the reaction time is 80 minutes, the stirring speed is 430 revolutions per minute, hydrogen is required to be introduced into a slurry bed catalytic cracking reactor B in the reaction, the hydrogen partial pressure is 5.8MPa, and the products after the reaction are separated to obtain a liquid product i, a gas i and an insoluble substance i; and cooling the obtained liquid product i to room temperature, sequentially introducing tetrahydrofuran and a cyclohexane solvent for extraction to obtain a tetrahydrofuran solution containing the liquid product ii, a cyclohexane solution containing the liquid product iii and the residual liquid product iv, and distilling the tetrahydrofuran solution containing the liquid product ii and the cyclohexane solution containing the liquid product iii to remove the solvent to obtain the liquid product ii and the liquid product iii.
Adding the residual liquid product III, the residual liquid product iv, the insoluble substance I and the insoluble substance I into a slurry bed catalytic cracking reactor C for deep catalytic cracking reaction, taking the phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve prepared by the method as a catalyst CAT-A, wherein the usage amount of the catalyst is 12% of the total mass of all reaction materials added into the slurry bed catalytic cracking reactor C, and performing the deep catalytic cracking reaction under the following reaction conditions: the reaction temperature is 570 ℃, the reaction time is 100 minutes, the stirring speed is 440 r/min, hydrogen is required to be introduced into a slurry bed catalytic cracking reactor C in the reaction, the hydrogen partial pressure is 7.0MPa, and the obtained cracking product is separated to obtain a liquid product V, a gas V and an insoluble substance V; and cooling the obtained liquid product V, sequentially introducing tetrahydrofuran and a cyclohexane solvent for extraction to respectively obtain a tetrahydrofuran solution containing a liquid product VI, a cyclohexane solution containing a liquid product VII and the residual liquid product VIII, and removing the solvent by distillation treatment to obtain the liquid product VI and the liquid product VII.
Example 2
Except that the reaction conditions of the catalytic cracking reaction carried out in the slurry bed catalytic cracking reactor a in example 1 were changed to: the reaction temperature is 453 ℃, the reaction time is 110 minutes, the stirring speed is 480 revolutions per minute, hydrogen needs to be introduced into the slurry bed catalytic cracking reactor A in the reaction, the hydrogen partial pressure is 3.2MPa, and the conditions for carrying out deep catalytic cracking reaction by the slurry bed catalytic cracking reactor C are changed as follows: the reaction temperature is 590 ℃, the reaction time is 80 minutes, the stirring speed is 500 r/min, hydrogen is required to be introduced into the slurry bed catalytic cracking reactor C in the reaction, and the hydrogen partial pressure is 7.0 MPa.
Example 3
except that the catalyst 1-a in example 1 was replaced with the catalyst 1-B, and "iron naphthenate and molybdenum naphthenate were added to the slurry bed catalytic cracking reactor B so that the slurry bed catalytic cracking reactor B contained 500ppm by mass of each of iron naphthenate and molybdenum naphthenate" was replaced with: the procedure of example 1 was repeated except that iron naphthenate was added to the slurry bed catalytic cracking reactor B so that the slurry bed catalytic cracking reactor B contained 1000ppm of iron naphthenate in total.
Example 4
Except that the catalyst 1-a in example 1 was replaced with the catalyst 1-C, and "iron naphthenate and molybdenum naphthenate were added to the slurry bed catalytic cracking reactor B so that the slurry bed catalytic cracking reactor B contained 500ppm by mass of each of iron naphthenate and molybdenum naphthenate" was replaced with: molybdenum naphthenate was added to the slurry bed catalytic cracking reactor B so that the slurry bed catalytic cracking reactor B contained molybdenum naphthenate in an amount of 1000ppm in total, otherwise the same as in example 1.
example 5
The catalyst CAT-A in mutexample 1 was replaced with CAT-B, and the procedure was otherwise the same as in mutexample 1.
Comparative example 1
Taking 2g of a mixture of three plastics of 50 wt% HDPE, 30 wt% PET and 20 wt% PS, crushing 3g of straws into powder with the length of about 10mm, adding the powder into a slurry bed catalytic cracking reactor together, and carrying out catalytic cracking reaction under the catalytic action of an HY molecular sieve catalyst, wherein the addition amount of the HY molecular sieve is 12% of the total mass of the waste plastics and cellulose, and the reaction conditions of the catalytic cracking reaction are as follows: the reaction temperature is 520 ℃, the reaction time is 70 minutes, the stirring speed is 430 revolutions per minute, hydrogen needs to be introduced into a catalytic cracking reactor of a slurry bed in the reaction, the hydrogen partial pressure is 5.6MPa, and the products after the reaction are separated to obtain a liquid product 1, gas and waste residues; and cooling the liquid product 1 to room temperature, sequentially introducing tetrahydrofuran and a cyclohexane solvent for extraction to respectively obtain a tetrahydrofuran solution containing the liquid product 2, a cyclohexane solution containing the liquid product 3 and a residual liquid product IV, and distilling the tetrahydrofuran solution containing the liquid product 2 and the cyclohexane solution containing the liquid product 3 to remove the solvent to obtain the liquid product 2 and the liquid product 3.
TABLE 1 comparison of the distribution and conversion of the products obtained in examples 1-5 and comparative example 1
| Numbering | Example 1 | example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Product distribution, wt% | ||||||
| Gas (es) | 4.3 | 6.8 | 6.3 | 7.8 | 9.5 | 13.3 |
| Soluble cyclohexane | 35.2 | 36.4 | 34.7 | 34.6 | 28.1 | 19.6 |
| Soluble matter of tetrahydrofuran | 49.5 | 48.3 | 43.4 | 43.3 | 38.7 | 23.4 |
| Residue of | 11.0 | 8.5 | 15.6 | 14.3 | 23.7 | 43.7 |
| Conversion in wt.% | 89.0 | 91.5 | 84.4 | 85.7 | 76.3 | 56.3 |
Claims (18)
1. a method of processing waste plastic and fiber comprising the steps of:
(1) Waste plastics are added into a catalytic reactor A, catalytic cracking reaction is carried out under the action of a catalyst 1, and the obtained cracking product is separated to obtain a liquid product I, a gas I and insoluble substances I;
(2) cooling the liquid product I obtained in the step (1), and introducing a tetrahydrofuran and cyclohexane mixed solvent for extraction to respectively obtain a tetrahydrofuran and cyclohexane mixed solvent containing a liquid product II and a residual liquid product III;
(3) Adding cellulose and the mixed solvent of tetrahydrofuran and cyclohexane containing the liquid product II obtained in the step (2) into a catalytic reactor B for catalytic reaction, and separating to obtain a liquid product i, a gas i and an insoluble substance i;
(4) Cooling the liquid product i obtained in the step (3), sequentially introducing tetrahydrofuran and a cyclohexane solvent for extraction to respectively obtain a tetrahydrofuran solution containing the liquid product ii, a cyclohexane solution containing the liquid product iii and a residual liquid product iv, and removing the solvent through distillation treatment to obtain a liquid product ii and a liquid product iii;
(5) Adding the residual liquid product III and the residual liquid product iv obtained in the step (2) and the step (4) and the insoluble substance I and the insoluble substance I obtained in the step (1) and the step (3) into a catalytic reactor C, carrying out deep catalytic cracking reaction under the action of a catalyst 2, and separating the obtained cracking product to obtain a liquid product V, a gas V and an insoluble substance V;
(6) Cooling the liquid product V obtained in the step (5), sequentially introducing tetrahydrofuran and cyclohexane solvent for extraction to respectively obtain a tetrahydrofuran solution containing a liquid product VI, a cyclohexane solution containing a liquid product VII and a residual liquid product VIII, and removing the solvent through distillation treatment to obtain a liquid product VI and a liquid product VII;
Wherein, the catalyst 1 in the step (1) consists of two catalysts, one is iron naphthenate and/or molybdenum naphthenate, and the other is an HY molecular sieve catalyst; and (3) the catalyst 2 in the step (5) is an HZSM-5 and HY composite molecular sieve catalyst.
2. the method according to claim 1, wherein the waste plastics of step (1) comprise one or more of polyethylene plastics, polypropylene plastics, and polystyrene in a total amount of not less than 80% by mass of the total amount of the waste plastics added.
3. The method according to claim 1, wherein the catalyst 1 in the step (1) has a mass ratio of the iron naphthenate and/or the molybdenum naphthenate to the HY molecular sieve catalyst of 0.1 to 0.5: 1; the usage amount of the catalyst 1 is 5-20% of the total mass of the added waste plastics.
4. The method according to claim 3, wherein the mass ratio of the iron naphthenate and/or molybdenum naphthenate to the HY molecular sieve catalyst in the catalyst 1 in the step (1) is 0.1-0.2: 1.
5. a method according to claim 3, characterized in that the catalyst 1 of step (1) is used in an amount of 10% to 15% of the total mass of added waste plastics.
6. The method according to claim 1, wherein the catalytic cracking reaction of step (1) is carried out under the following reaction conditions: the reaction temperature is 350-550 ℃, the reaction time is 30-150 minutes, the reaction is carried out under stirring, and the stirring speed is 350-600 revolutions per minute; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 2-4 MPa.
7. the method according to claim 6, wherein the catalytic cracking reaction of step (1) is carried out under the following reaction conditions: the reaction temperature is 400-; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 2.5-3.5 MPa.
8. The method according to claim 1, wherein the cellulose in the step (3) is one or more of straw, bark and straw; before the cellulose is added into the catalytic reactor B, the cellulose is pretreated, wherein the pretreatment comprises at least one of crushing treatment and dehydration treatment, the length of the cellulose material after the crushing treatment is not more than 20mm, the dehydration treatment is carried out under the anaerobic condition, the treatment temperature is 100-200 ℃, and the treatment time is 60-120 minutes.
9. the process according to claim 1, wherein the cellulose is added in step (3) while a sulfur source having a mass content of 4000-: 1, the selected sulfur sources are as follows: one or more of sulfur, hydrogen sulfide and carbon disulfide.
10. The method according to claim 1, wherein the reaction conditions of the catalytic reaction in the step (3) are as follows: the reaction temperature is 400-600 ℃, the reaction time is 30-100 minutes, the reaction is carried out under stirring, and the stirring speed is 350-600 revolutions per minute; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 4-8 MPa.
11. The method according to claim 10, wherein the reaction conditions of the catalytic reaction in the step (3) are as follows: the reaction temperature is 450-550 ℃; the reaction time is 60-100 minutes; the reaction is carried out under stirring, and the stirring speed is 400-500 r/min; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 5-6.5 MPa.
12. The method according to claim 10 or 11, wherein the reaction temperature of the catalytic reaction in step (3) is at least 50 ℃ higher than the reaction temperature of the catalytic reaction in step (1), and the hydrogen partial pressure of the catalytic reaction in step (3) is at least 2MPa higher than the hydrogen partial pressure of the catalytic reaction in step (1).
13. The method according to claim 1, wherein the catalyst 2 in the step (5) is a phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst, wherein the mass content of phosphorus is 1.5% -7.0%, and the mass content of tungsten is 0.3% -2.0%; the usage amount of the catalyst 2 is 5-20% of the total mass of all the added reaction materials added into the catalytic reactor C in the step (5).
14. The process according to claim 13, characterized in that the catalyst 2 in step (5) is used in an amount of 10% to 15% by mass based on the total mass of all the reactants charged into the catalytic reactor C in step (5).
15. The method according to claim 13, wherein the catalyst 2 of step (5) is prepared by: mixing HZSM-5 and HY according to the mass ratio of 0.5-2:1 to obtain a composite molecular sieve, impregnating the composite molecular sieve with a phosphoric acid solution with the mass concentration of 10% -20%, wherein the mass ratio of the phosphoric acid solution to the composite molecular sieve is 0.5-1:1, drying at 80-110 ℃ for 1-3 hours, impregnating the composite molecular sieve with a sodium tungstate solution with the mass concentration of 1% -2%, wherein the mass ratio of the sodium tungstate solution to the composite molecular sieve is 0.5-1:1, drying at 80-110 ℃ for 5-10 hours, roasting at 330 ℃ and 380 ℃ for 4-7 hours, and forming to obtain a catalyst 2.
16. the method according to claim 1, wherein the reaction conditions of the deep catalytic cracking reaction of step (5) are: the reaction temperature is 400-700 ℃, and the reaction time is 60-150 minutes; the reaction is carried out under stirring, and the stirring speed is 350-600 revolutions per minute; hydrogen is needed to be introduced in the reaction, and the hydrogen partial pressure is 5-10 MPa.
17. The method as set forth in claim 16, characterized in that the reaction temperature of the deep catalytic cracking reaction in the step (5) is 500-600 ℃.
18. The method according to claim 16 or 17, wherein the reaction temperature of the catalytic reaction in step (5) is at least 50 ℃ higher than the reaction temperature of the catalytic reaction in step (3), and the hydrogen partial pressure of the catalytic reaction in step (5) is at least 1MPa higher than the hydrogen partial pressure of the catalytic reaction in step (3).
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| CN1462790A (en) * | 2003-05-26 | 2003-12-24 | 四川大学 | Catalyst for cracking waste plastics to generate fuel |
| WO2007086348A1 (en) * | 2006-01-26 | 2007-08-02 | Kitakyushu Foundation For The Advancement Of Industry, Science And Technology | Process and apparatus for the catalytic cracking of waste plastics |
| CN101265412A (en) * | 2008-04-09 | 2008-09-17 | 江华鹏 | Method for preparing fuel oil by biomass and waste plastic copyrolysis |
| CN104888860A (en) * | 2015-05-26 | 2015-09-09 | 中国石油大学(华东) | Naphthenate catalyst, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1462790A (en) * | 2003-05-26 | 2003-12-24 | 四川大学 | Catalyst for cracking waste plastics to generate fuel |
| WO2007086348A1 (en) * | 2006-01-26 | 2007-08-02 | Kitakyushu Foundation For The Advancement Of Industry, Science And Technology | Process and apparatus for the catalytic cracking of waste plastics |
| CN101265412A (en) * | 2008-04-09 | 2008-09-17 | 江华鹏 | Method for preparing fuel oil by biomass and waste plastic copyrolysis |
| CN104888860A (en) * | 2015-05-26 | 2015-09-09 | 中国石油大学(华东) | Naphthenate catalyst, and preparation method and application thereof |
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