CN108329514A - The method for processing waste plastics and cellulose - Google Patents
The method for processing waste plastics and cellulose Download PDFInfo
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- CN108329514A CN108329514A CN201810142826.XA CN201810142826A CN108329514A CN 108329514 A CN108329514 A CN 108329514A CN 201810142826 A CN201810142826 A CN 201810142826A CN 108329514 A CN108329514 A CN 108329514A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J11/16—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 inorganic material
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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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- C08J2325/06—Polystyrene
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention discloses a kind of methods of processing waste plastics and cellulose.This method includes：Waste plastics is through the product obtained by iron naphthenate and/or molybdenum naphthenate and HY molecular sieve catalyst catalytic pyrolysis,It is isolated to product liquid I,Gas I and insoluble matter I,Product liquid I is through tetrahydrofuran and thiacyclohexane mixed solvent,The mixed solvent of product liquid II must be contained,Remaining product liquid III,The former carries out catalysis with cellulose and reacts,It is isolated to product liquid i,Gas i and insoluble matter i,Product liquid i extracts to obtain product liquid ii and product liquid iii and remaining product liquid iv through tetrahydrofuran and thiacyclohexane respectively,By product liquid III,Product liquid iv and insoluble matter I and insoluble matter i carry out Deep catalytic cracking reaction,Products therefrom is detached through gas-liquid-solid,The product liquid V of separation is respectively through tetrahydrofuran and thiacyclohexane extraction and separation,Obtain product liquid VI and product liquid VII.This method not only increases overall conversion, and promotes the progress of goal response to improve liquid yield.
Description
Technical field
The invention belongs to fixed-end forces technical field, more particularly to a kind of method of processing waste plastics and cellulose.
Background technology
The rubbish that the use of a large amount of plastic products generates not only has seriously polluted the environment, but also causes the waste of resource.
Currently, plastic products consumption figure is huge, can all generate a large amount of waste plastic every year, but the recycling of waste plastics at present collect with
And classification effectiveness is generally relatively low, it is difficult to the various waste plastics of lasting supply, therefore individually treatment of waste plastics is hardly formed
Scale continuous production.Although the yield of cellulose is larger, it is at present much directly to incinerate, causes a large amount of air pollution
With the waste of resource.The liquefaction technology of plastics and the Optimum utilization of cellulose have had some researchs at present, if useless modeling
Material is added in cellulose copyrolysis processing together, can utilize the advantage of the two pyrolysis so that the production of the two valuable product
Amount is more increased.However, people to plastics and cellulose respectively direct liquefaction the study found that the reaction condition needed for the two and catalysis
The process conditions gap such as agent is larger, and directly waste plastics and cellulose liquefy together, to the type of reactant, reaction condition, urges
Agent etc. has higher requirement, this is jointly processed by waste plastics and cellulose with certain challenge.
Invention content
Aiming at the deficiencies in the prior art, the present invention provides a kind of methods of processing waste plastics and cellulose.It should
Method not only increases overall conversion ratio, and promote target compared with the treatment process of existing waste plastics and cellulose
The progress of reaction improves the economic benefit and environmental benefit of entire technique to improve liquid yield.
The method of a kind of processing waste plastics and cellulose provided by the invention, includes the following steps：
(1) waste plastics is added in catalytic reactor A, catalytic cracking reaction, gained is carried out under the action of catalyst 1
Pyrolysis product be isolated to product liquid I, gas I and insoluble matter I；
(2) the product liquid I obtained by step (1) is passed through tetrahydrofuran after cooling and hexamethylene mixed solvent is extracted
It takes, respectively obtains the tetrahydrofuran and hexamethylene mixed solvent, remaining product liquid III of the II containing product liquid；
(3) by the tetrahydrofuran solution and hexamethylene mixed solvent of the II containing product liquid obtained by cellulose and step (2)
It is added in catalytic reactor B, carries out catalysis reaction, be isolated to product liquid i, gas i and insoluble matter i；
(4) by the product liquid i obtained by step (3) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts
It takes, respectively obtains the tetrahydrofuran solution of the ii containing product liquid, the cyclohexane solution of the iii containing product liquid and the production of remaining liquid
Object iv obtains product liquid ii and product liquid iii by distilling processing to remove solvent；
(5) remaining product liquid III, remaining product liquid iv and the step that step (2) and step (4) are respectively obtained
Suddenly the insoluble matter I and insoluble matter i that (1) and step (3) respectively obtain are added in catalytic reactor C, under the action of catalyst 2
Deep catalytic cracking reaction is carried out, the pyrolysis product of gained is isolated to product liquid V, gas V and insoluble matter V；
(6) by the product liquid V obtained by step (5) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts
It takes, respectively obtains the tetrahydrofuran solution of the VI containing product liquid, the cyclohexane solution of the VII containing product liquid and the production of remaining liquid
Object VIII obtains product liquid VI and product liquid VII by distilling processing to remove solvent；
Wherein, the catalyst agent 1 described in step (1) is made of two kinds of catalyst, and one is iron naphthenate and/or aphthenic acids
Molybdenum, secondly being HY molecular sieve catalysts.
In the present invention, described catalytic reactor A, B and C are slurry bed system catalytic cracking reaction device.
In the present invention, the waste plastics described in step (1) includes mainly polyethylene (PE), PP type plastics
(PP), the mixture of one or more of polystyrene (PS), 80% of total content not less than addition waste plastics gross mass.
In the present invention, iron naphthenate and/or molybdenum naphthenate and HY molecular sieve catalysts in the catalyst 1 described in step (1)
Mass ratio be 0.1-0.5:1, preferably 0.1-0.3:1.
In the present invention, the usage amount that the catalyst 1 described in step (1) is is the 5%-20% of added waste plastics gross mass,
Preferably 10%-15%.
In the present invention, the reaction condition of the catalytic cracking reaction described in step (1) is as follows：Reaction temperature is 350-550 DEG C,
Preferably 400-480 DEG C；Reaction time is 30-150 minutes, preferably 45-120 minutes；Reaction carries out under stiring, stirring speed
Rate is 350-600 revs/min, preferably 400-500 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 2-4MPa is excellent
It is selected as 2.5-3.5MPa.
In the present invention, the mass ratio 1-3 of tetrahydrofuran and hexamethylene mixed solvent and product liquid I described in step (2):
1, the wherein mass ratio of tetrahydrofuran and hexamethylene is 1-3:1, preferably 1-2:1.
In the present invention, the cooling described in step (2), step (4) and step (6) is preferably cold by product liquid I, product liquid
I and product liquid V is but to room temperature.
In the present invention, the distillation processing described in step (4) and step (6) is the distillating method of this field routine, to remove
Tetrahydrofuran or thiacyclohexane solvent.
In the present invention, the cellulose described in step (3) is one kind in the plant fibers substances such as stalk, bark, straw
Or it is several.
In the present invention, the cellulose described in step (3) is added to before catalytic reactor B, preferably through pretreatment, such as powder
At least one of broken, dehydration.Wherein the crushing, the powder obtained by crushing, length are preferably more than
20mm.The dehydration carries out under anaerobic, and treatment temperature is 100-200 DEG C, processing time 60-120
Minute.
The tetrahydrofuran solution and hexamethylene of the II containing product liquid obtained by step (2) are added in the present invention, in step (3)
The tetrahydrofuran solution and hexamethylene mixed solvent mass ratio of mixed solvent, cellulose and the II containing product liquid are 0.8-1.2:1.
In the present invention, a certain amount of iron naphthenate and/or molybdenum naphthenate can be added in step (3) as needed, and satisfaction makes
The gross mass content of iron and molybdenum is 800-1200ppm in catalytic reactor B.Quality is added while cellulose is added in step (3)
Content is calculated as the sulphur source of 4000-8000ppm as vulcanizing agent using sulphur, sulfur content and iron and molybdenum total content in catalytic reactor B
Mass ratio is 5-7：1, wherein selected sulphur source is one or more in sulphur, hydrogen sulfide, carbon disulfide etc..
In the present invention, the reaction condition of the catalysis reaction described in step (3) is as follows：Reaction temperature is 400-600 DEG C, preferably
It is 450-550 DEG C；Reaction time is 30-100 minutes, preferably 60-100 minutes；Reaction carries out under stiring, and stir speed (S.S.) is
350-600 revs/min, preferably 400-500 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 4-8MPa, preferably
5-6.5MPa.Further, it is preferable to reaction condition it is as follows：The reaction temperature of step (3) the catalysis reaction is than step (1) institute
The reaction temperature for stating catalysis reaction is at least 50 DEG C high, and the hydrogen partial pressure catalysis more described than step (1) of step (3) the catalysis reaction is anti-
At least high 2MPa of the hydrogen partial pressure answered.
In the present invention, catalyst 2 described in step (5) is HZSM-5 and HY composite molecular sieve catalysts, HZSM-5 with
The mass ratio 0.5-2 of HY：1, the HZSM-5 and HY composite molecular sieve catalysts, the quality of wherein phosphorus that preferably phosphorus and tungsten are modified contain
Amount is 1.5%~7.0%, and the mass content of tungsten is 0.3%~2.0%.The usage amount of the catalyst 2 is to add in step (5)
Enter the 5%-20% of reaction mass gross mass added by the whole in catalytic reactor C, preferably 10%-15%.
In the present invention, the preparation method of used catalyst 2 is preferably as follows：HZSM-5 and HY carries out being mixed to get compound molecule
Sieve, the phosphoric acid solution for being 10%~20% with mass concentration impregnates composite molecular screen, 1-3 hours dry at 80-110 DEG C；With
The wolframic acid sodium water solution that mass concentration is 1%~2% impregnates composite molecular screen again, 5-10 hours dry at 80-110 DEG C,
It is finally roasted 4-7 hours at 330-380 DEG C, catalyst 2 is obtained after molding.
In the present invention, conventional method molding, such as compression molding etc. may be used in the catalyst 2, in forming process
Shaping assistant can be added as needed.It after compression molding, is sieved as needed, takes granular size for 30 mesh to 70
Mesh, preferably the solid particle of 40 to 60 mesh is as catalyst 2.The phosphorus and tungsten modified HZSM-5 is catalyzed with HY composite molecular screens
In agent phosphorus there may be form be it is one or more in phosphotungstic acid, the oxide of phosphorus, phosphotungstate, phosphoric acid, phosphate etc.,
Tungsten is one or more in phosphotungstic acid, the oxide of tungsten, phosphotungstate etc. there may be form, it is preferred to use the above method
The catalyst of preparation.
In the present invention, the reaction condition of step (5) the Deep catalytic cracking reaction is：Reaction temperature is 400-700 DEG C,
Preferably 500-600 DEG C；Reaction time is 60-150 minutes；Reaction carries out under stiring, and stir speed (S.S.) is 350-600 revs/min
Clock；Need to be passed through hydrogen, hydrogen partial pressure 5-10MPa in reaction.Further, it is preferable to reaction condition it is as follows：Step (5) institute
The reaction temperature for stating the reaction temperature catalysis reaction more described than step (3) of catalysis reaction is at least 50 DEG C high, step (5) described catalysis
At least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure of the reaction catalysis reaction more described than step (3).
Compared with prior art, the present invention has the following advantages：
As two kinds of intractable solid waste rubbish, the present invention is by the processing of cellulose and gives up for cellulose and waste plastics
The catalytic pyrolysis of plastics is combined, while they are turned waste into wealth.The present invention makes full use of the characteristics of two kinds of reactions, reacts item
Part each self-optimizing again not only increases overall conversion ratio, and promote compared with conventional waste plastics and cellulose coprocessing
The progress of goal response reduces insoluble object amount to improving the yield of hexamethylene soluble matter and tetrahydrofuran soluble matter.
Especially use iron naphthenate and/or molybdenum naphthenate, HY molecular sieves as catalyst waste plastics catalytic pyrolysis, after by tetrahydrochysene furan
The product liquid being obtained by extraction of muttering is pyrolyzed jointly with cellulose, is not only facilitated and is improved polarity production in cellulose catalytic reaction process
The dissolving of object improves the conversion ratio of cellulose, also saves cost.In addition, the present invention reacts waste plastics and cellulose through catalysis
Insoluble matter afterwards collects mixing, and is not remained by what tetrahydrofuran and hexamethylene extracted after waste plastics and cellulose catalytic reaction is added
Remaining product liquid carries out Deep catalytic cracking reaction, reduces the generation of a large amount of waste residues under the effect of the catalyst.For more difficult
The waste residue of processing, the HZSM-5 and HY composite molecular sieve catalysts that phosphorus and tungsten especially with the present invention are modified, cracking temperature
It is more mild, and cleavage rate is high.
In addition, present invention process flow is simple, reaction condition is mild, simple and practicable, and cost is relatively low, solves a large amount of useless modelings
Material and cellulose processing hardly possible, recycling are worth low problem, not only slow down environment caused by a large amount of waste plastics and cellulose
Pressure, and turn waste into wealth, hence it is evident that improve the surcharge of waste plastics and cellulose.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention；
The reference numerals are as follows：1, catalytic reactor A；2, gas-liquid-solid separator a；3, be equipped with successively with tetrahydrofuran and
Hexamethylene is the extraction equipment a of solvent；4, catalytic reactor B；5, gas-liquid solid separation device b；6, it is equipped with successively with tetrahydrofuran
With the extraction equipment b that hexamethylene is solvent；7, catalytic reactor C；8, gas-solid separating device c；9, it is equipped with successively with tetrahydrofuran
With the extraction equipment c that hexamethylene is solvent；21, liquid product I；22, gas I；23 insoluble matter I；31, four of the II containing product liquid
Hydrogen furans and hexamethylene mixed solvent；32, remaining product liquid III；51, product liquid i；52, gas i；53, insoluble matter i；
61, product liquid ii；62, product liquid iii；63, remaining product liquid iv；81, product liquid V；82, gas V；83, no
Molten object V；91, product liquid VI；92, product liquid VII；93, remaining product liquid VIII.
Specific implementation mode
The method for further illustrating the present invention processing waste plastics and cellulose with reference to specific embodiment, but this
The protection domain of invention and the range for being not so limited to following embodiment.In the present invention, wt% representation quality scores.
As shown in Figure 1, the method for processing waste plastics and cellulose provided by the invention, includes the following steps：
(1) waste plastics is added in catalytic reactor A1, catalytic cracking reaction, institute is carried out under the action of catalyst 1
The pyrolysis product obtained obtains product liquid I 21, gas I 22 and insoluble matter I 23 through gas-liquid-solid separator a 2；
(2) the product liquid I 21 obtained by step (1) is passed through after cooling equipped with molten with tetrahydrofuran and hexamethylene mixing
Agent is that the extraction equipment a 3 of solvent is extracted, and respectively obtains the tetrahydrofuran and hexamethylene mixed solvent of the II containing product liquid
31, remaining product liquid III 32；
(3) cellulose is charged first in catalytic reactor B 4 and is carried out dehydrating, then added obtained by step (2)
The II containing product liquid tetrahydrofuran and hexamethylene mixed solvent 31, be added sulphur source carry out catalysis reaction, detached through gas-liquid-solid
5 isolated product liquid i 51 of device b, gas i 52 and insoluble matter i 53；
(4) the product liquid i 51 obtained by step (3) is passed through successively after cooling equipped with tetrahydrofuran and hexamethylene
It is extracted for the extraction equipment b 6 of solvent, respectively obtains tetrahydrofuran solution, the iii containing product liquid of the ii containing product liquid
Cyclohexane solution and remaining product liquid iv 63, by distill processing to remove solvent, obtain 61 Hes of product liquid ii
Product liquid iii 62；
(5) remaining product liquid III 32, the remaining product liquid iv that step (2) and step (4) are respectively obtained
63 and step (1) and step (3) the insoluble matter I 23 that respectively obtains and insoluble matter I 53 be added in catalytic reactor C 7,
Deep catalytic cracking reaction is carried out under the action of catalyst 2, the pyrolysis product of gained is isolated through gas-liquid solid separation device c 8
Product liquid V 81, gas V 82 and insoluble matter V 83；
(6) the product liquid V81 obtained by step (5) is passed through after cooling to be equipped with tetrahydrofuran and hexamethylene successively and is
The extraction equipment c 9 of solvent is extracted, and the tetrahydrofuran solution of the VI containing product liquid, the VII containing product liquid are respectively obtained
Cyclohexane solution and remaining product liquid VIII 93 obtain 91 Hes of product liquid VI by distilling processing to remove solvent
Product liquid VII 92.
Wherein, insoluble matter V 83 is the waste residue for not continuing to participate in reaction, and remaining product liquid VIII 93 can be recycled
Further catalytic cracking reaction is carried out to catalytic reactor C 7.
Wherein, product is gas, hexamethylene soluble matter, tetrahydrofuran soluble matter, waste residue in table 1, wherein gas is gas
I 22, gas i 52 and gas V82, thiacyclohexane soluble matter are product liquid iii 62 and product liquid VII 92, tetrahydrofuran
Soluble matter is product liquid ii 61 and product liquid VI 91, and residue is insoluble matter V 83 and remaining product liquid VIII
93.Conversion ratio refers to that gas in product, hexamethylene soluble matter, tetrahydrofuran soluble matter gross mass account for the hundred of four kinds of product qualities
Score.In the present invention, gas is mainly four low-carbon alkene below of the carbon such as ethylene and propylene.
Catalyst 1-A used in the embodiment of the present invention：It is made of two kinds of catalyst, one is iron naphthenate and aphthenic acids
Molybdenum, secondly being HY molecular sieve catalysts.By weight, the mass ratio of iron naphthenate and molybdenum naphthenate and HY molecular sieve catalysts is
0.15:1, and the mass ratio of iron naphthenate and molybdenum naphthenate is 1:1.
Catalyst 1-B used in the embodiment of the present invention：It is made of two kinds of catalyst, one is iron naphthenate, secondly being HY
Molecular sieve catalyst.By weight, the mass ratio of iron naphthenate and HY molecular sieve catalysts is 0.18:1.
Catalyst 1-C used in the embodiment of the present invention：It is made of two kinds of catalyst, one is molybdenum naphthenate, secondly being HY
Molecular sieve catalyst is by weight.By weight, the mass ratio of molybdenum naphthenate and HY molecular sieve catalysts is 0.12:1.
The HZSM-5 and HY composite molecular sieve catalysts CAT-A that phosphorus used in the embodiment of the present invention and tungsten are modified is specifically such as
Under：The mass ratio of HZSM-5 and HY composite molecular screens is 1：1, the mass content of phosphorus is 3%, and the mass content of tungsten is 1.2%,
Preparation method is as follows：HZSM-5 is mixed with HY molecular sieves, and the phosphoric acid solution for being 15% with mass concentration impregnates compound molecule
Sieve, it is 2 hours dry at 100 DEG C；The wolframic acid sodium water solution for being 1.5% with mass concentration impregnates composite molecular screen, at 100 DEG C
It is 8 hours dry, it is finally roasted 6 hours at 350 DEG C, through compression molding, sieving, it is the solid of 40 mesh to 60 mesh to take granular size
The HZSM-5 and HY composite molecular sieve catalysts CAT-A that particle is modified as phosphorus and tungsten.
HZSM-5 and HY composite molecular sieve catalysts CAT-B used in the embodiment of the present invention is specific as follows：HZSM-5 and HY
The mass ratio of composite molecular screen is 1：1, preparation method is as follows：HZSM-5 is mixed with HY composite molecular screens, at 100 DEG C
It is 8 hours dry, it is finally roasted 6 hours at 350 DEG C, through compression molding, sieving, it is the solid of 40 mesh to 60 mesh to take granular size
Particle is as HZSM-5 and HY composite molecular sieve catalysts CAT-B.
Embodiment 1
The total 2g of mixture for choosing three kinds of plastics of 50wt%HDPE, 30wt%PET, 20wt%PS is reacted as waste plastics
Raw material, add it in slurry bed system catalytic cracking reaction device A, under catalyst 1-A catalytic action carry out catalytic pyrolysis it is anti-
It answers, the additive amount of catalyst 1-A is the 12% of waste plastics gross mass, and the reaction condition of catalytic cracking reaction is as follows：Reaction temperature
It it is 435 DEG C, the reaction time is 80 minutes, and stir speed (S.S.) is 440 revs/min, needs to be passed through hydrogen into catalytic reactor A in reaction
Gas, hydrogen partial pressure 2.8MPa detach the product after reaction, obtain product liquid I, gas I and insoluble matter I；By liquid
Product I is passed through tetrahydrofuran after being cooled to room temperature and hexamethylene mixed solvent is extracted, tetrahydrofuran and hexamethylene mixing
The mass ratio of solvent and product liquid I are 1.5:1, the wherein mass ratio of tetrahydrofuran and hexamethylene is 2:1, it respectively obtains containing liquid
Tetrahydrofuran and hexamethylene mixed solvent, the remaining liquid product III of body product II；3g stalks, which are crushed to length, is about
The powder of 10mm, is then carried out dehydrating under anaerobic, and treatment temperature is 130 DEG C, and processing time is 70 minutes, pre- to locate
Stalk after reason is added in slurry bed system catalytic cracking reaction device B, and by the tetrahydrofuran and hexamethylene of the II containing product liquid
Mixed solvent is passed through slurry bed system catalytic cracking reaction device B, then into slurry bed system catalytic cracking reaction device B be added iron naphthenate and
Molybdenum naphthenate makes the iron naphthenate containing each 500ppm of mass content and molybdenum naphthenate in slurry bed system catalytic cracking reaction device B urge
Agent, while sulphur that mass content is 6000ppm is added as vulcanizing agent, make sulfur content and iron and molybdenum in catalytic reactor B
The mass ratio of total content is 6：1, then reacted under following reaction condition：Reaction temperature is 515 DEG C, the reaction time 80
Minute, stir speed (S.S.) is 430 revs/min, and the needs in reaction are passed through hydrogen, hydrogen point into slurry bed system catalytic cracking reaction device B
Pressure is 5.8MPa, is detached to the product after reaction, obtains product liquid i, gas i and insoluble matter i；The liquid of gained is produced
Object i is passed through tetrahydrofuran successively after being cooled to room temperature and cyclohexane solvent is extracted, and obtains the tetrahydrochysene furan of the ii containing product liquid
Mutter solution and cyclohexane solution and the remaining product liquid iv of the iii containing product liquid, and to the tetrahydrochysene furan of the ii containing product liquid
The cyclohexane solution of solution and the iii containing product liquid of muttering carries out distillation processing to remove solvent, obtains product liquid ii and liquid
Product iii.
Remaining product liquid III, remaining product liquid iv and insoluble matter I and insoluble matter i are added to slurry bed system and urged
Change and carry out Deep catalytic cracking reaction in cracking reactor C, the HZSM-5 and HY that phosphorus and tungsten prepared by method described above is modified is multiple
Molecular sieve is closed as catalyst CAT-A, the usage amount of the catalyst is all anti-in addition slurry bed system catalytic cracking reaction device C
The 12% of material gross mass is answered, Deep catalytic cracking reaction is carried out under following reaction condition：Reaction temperature is 570 DEG C, reaction
Time is 100 minutes, and 440 revs/min of stir speed (S.S.), the needs in reaction are passed through hydrogen into slurry bed system catalytic cracking reaction device C
The pyrolysis product of gas, hydrogen partial pressure 7.0MPa, gained is isolated to product liquid V, gas V and insoluble matter V；By gained
Product liquid V is passed through tetrahydrofuran successively after cooling, cyclohexane solvent is extracted, and respectively obtains four of the VI containing product liquid
Hydrogen tetrahydrofuran solution, the cyclohexane solution of the VII containing product liquid and remaining product liquid VIII, it is molten to remove by distilling processing
Agent obtains product liquid VI and product liquid VII.
Embodiment 2
Only the reaction condition of the catalytic cracking reaction carried out in slurry bed system catalytic cracking reaction device A in embodiment 1 is changed
For：Reaction temperature is 453 DEG C, and the reaction time is 110 minutes, and stir speed (S.S.) is 480 revs/min, is needed in reaction to slurry bed system
Hydrogen, hydrogen partial pressure 3.2MPa are passed through in catalytic cracking reaction device A, slurry bed system catalytic cracking reaction device C carries out Deep catalytic and splits
The condition of solution reaction is changed to：Reaction temperature is 590 DEG C, and the reaction time is 80 minutes, 500 revs/min of stir speed (S.S.), in reaction
It needs to be passed through hydrogen, hydrogen partial pressure 7.0MPa into slurry bed system catalytic cracking reaction device C.
Embodiment 3
Only change the catalyst 1-A in embodiment 1 into catalyst 1-B, and will be " to slurry bed system catalytic cracking reaction device B
Middle addition iron naphthenate and molybdenum naphthenate make the cycloalkanes containing each 500ppm of mass content in slurry bed system catalytic cracking reaction device B
Sour iron and molybdenum naphthenate " replaces with：Iron naphthenate is added into slurry bed system catalytic cracking reaction device B, makes slurry bed system catalytic pyrolysis
Altogether containing the iron naphthenate that mass content is 1000ppm, the other the same as in Example 1 in reactor B.
Embodiment 4
Only change the catalyst 1-A in embodiment 1 into catalyst 1-C, and will be " to slurry bed system catalytic cracking reaction device B
Middle addition iron naphthenate and molybdenum naphthenate make the cycloalkanes containing each 500ppm of mass content in slurry bed system catalytic cracking reaction device B
Sour iron and molybdenum naphthenate " replaces with：Molybdenum naphthenate is added into slurry bed system catalytic cracking reaction device B, makes slurry bed system catalytic pyrolysis
Altogether containing the molybdenum naphthenate that mass content is 1000ppm, the other the same as in Example 1 in reactor B.
Embodiment 5
Change the catalyst CAT-A in embodiment 1 into CAT-B, the other the same as in Example 1.
Comparative example 1
It takes the total 2g of mixture of three kinds of plastics of 50wt%HDPE, 30wt%PET, 20wt%PS, be crushed to 3g stalks
It is added in slurry bed system catalytic cracking reaction device, in the catalysis of HY molecular sieve catalysts by the powder of length about 10mm jointly
Effect is lower to carry out catalytic cracking reaction, and the additive amount of HY molecular sieves is the 12% of waste plastics and cellulose gross mass, catalytic pyrolysis
The reaction condition of reaction is as follows：Reaction temperature is 520 DEG C, and the reaction time is 70 minutes, and stir speed (S.S.) is 430 revs/min, reaction
In need to be passed through hydrogen into slurry bed system catalytic cracking reaction device, hydrogen partial pressure 5.6MPa detaches the product after reaction,
Obtain product liquid 1, gas and waste residue；Product liquid 1 is cooled to after room temperature and is passed through tetrahydrofuran, cyclohexane solvent successively
It is extracted, respectively obtains the tetrahydrofuran solution containing product liquid 2, the cyclohexane solution containing product liquid 3 and remaining liquid
State product IV, and the tetrahydrofuran solution containing product liquid 2, the cyclohexane solution containing product liquid 3 are distilled to remove
Solvent obtains product liquid 2 and product liquid 3.
The distribution of 1 embodiment 1-5 of table and 1 products therefrom of comparative example and conversion ratio comparison
| Number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Product is distributed, wt% | ||||||
| Gas | 4.3 | 6.8 | 6.3 | 7.8 | 9.5 | 13.3 |
| Hexamethylene soluble matter | 35.2 | 36.4 | 34.7 | 34.6 | 28.1 | 19.6 |
| Tetrahydrofuran soluble matter | 49.5 | 48.3 | 43.4 | 43.3 | 38.7 | 23.4 |
| Residue | 11.0 | 8.5 | 15.6 | 14.3 | 23.7 | 43.7 |
| Conversion ratio, wt% | 89.0 | 91.5 | 84.4 | 85.7 | 76.3 | 56.3 |
Claims (10)
1. a kind of method of processing waste plastics and fiber, includes the following steps：
(1) waste plastics is added in catalytic reactor A, catalytic cracking reaction is carried out under the action of catalyst 1, gained is split
Solution product is isolated to product liquid I, gas I and insoluble matter I；
(2) the product liquid I obtained by step (1) is passed through tetrahydrofuran after cooling and hexamethylene mixed solvent is extracted, point
The tetrahydrofuran and hexamethylene mixed solvent, remaining product liquid III of the II containing product liquid are not obtained；
(3) tetrahydrofuran of the II containing product liquid obtained by cellulose and step (2) and hexamethylene mixed solvent are added to catalysis
In reactor B, catalysis reaction is carried out, is isolated to product liquid i, gas i and insoluble matter i；
(4) by the product liquid i obtained by step (3) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts, point
The tetrahydrofuran solution of the ii containing product liquid, the cyclohexane solution of the iii containing product liquid and remaining product liquid iv are not obtained,
By distilling processing to remove solvent, product liquid ii and product liquid iii are obtained；
(5) remaining product liquid III, remaining product liquid iv and the step that step (2) and step (4) are respectively obtained
(1) be added in catalytic reactor C with step (3) the insoluble matter I that respectively obtains and insoluble matter i, under the action of catalyst 2 into
The pyrolysis product of row Deep catalytic cracking reaction, gained is isolated to product liquid V, gas V and insoluble matter V；
(6) by the product liquid V obtained by step (5) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts, point
The tetrahydrofuran solution of the VI containing product liquid, the cyclohexane solution of the VII containing product liquid and remaining product liquid are not obtained
VIII obtains product liquid VI and product liquid VII by distilling processing to remove solvent；
Wherein, the catalyst agent 1 described in step (1) is made of two kinds of catalyst, one be iron naphthenate and/or molybdenum naphthenate,
Secondly being HY molecular sieve catalysts.
2. according to the method for claim 1, it is characterised in that the waste plastics described in step (1) include polyethylene,
The mixture of one or more of PP type plastics, polystyrene, total content is not less than addition waste plastics gross mass
80%.
3. according to the method for claim 1, it is characterised in that iron naphthenate and/or ring in the catalyst 1 described in step (1)
The mass ratio of alkanoic acid molybdenum and HY molecular sieve catalysts is 0.1-0.5:1, preferably 0.1-0.2:1；The use of the catalyst 1
Amount is the 5%-20%, preferably 10%-15% of added waste plastics gross mass.
4. according to the method for claim 1, it is characterised in that the reaction condition of the catalytic cracking reaction described in step (1) is such as
Under：Reaction temperature is 350-550 DEG C, preferably 400-480 DEG C；Reaction time is 30-150 minutes, preferably 45-120 minutes；
Reaction carries out under stiring, and stir speed (S.S.) is 350-600 revs/min, preferably 400-500 revs/min；It needs to be passed through in reaction
Hydrogen, hydrogen partial pressure 2-4MPa, preferably 2.5-3.5MPa.
5. according to the method for claim 1, it is characterised in that the cellulose described in step (3) is stalk, bark, straw plant
One or more of fibres substance；The cellulose is added to before catalytic reactor B, is first pre-processed, described
Pretreatment includes at least one of pulverization process, dehydration, of length no more than 20mm of cellulose substances after pulverization process,
The dehydration carries out under anaerobic, and treatment temperature is 100-200 DEG C, and processing time is 60-120 minutes.
6. according to the method for claim 1, it is characterised in that step (3) be added cellulose while be added mass content with
Sulphur is calculated as the sulphur source of 4000-8000ppm as vulcanizing agent, the mass ratio of sulfur content and iron and molybdenum total content in catalytic reactor B
For 5-7：1, selected sulphur source has：It is one or more in sulphur, hydrogen sulfide, carbon disulfide.
7. according to the method for claim 1, it is characterised in that the reaction condition of the catalysis reaction described in step (3) is as follows：
Reaction temperature is 400-600 DEG C, preferably 450-550 DEG C；Reaction time is 30-100 minutes, preferably 60-100 minutes；Instead
It should carry out under stiring, stir speed (S.S.) is 350-600 revs/min, preferably 400-500 revs/min；It needs to be passed through hydrogen in reaction
Gas, hydrogen partial pressure 4-8MPa, preferably 5-6.5MPa；Further, it is preferable to reaction condition it is as follows：Step (3) described catalysis
The reaction temperature of the reaction temperature of the reaction catalysis reaction more described than step (1) is at least 50 DEG C high, step (3) the catalysis reaction
At least high 2MPa of hydrogen partial pressure of the hydrogen partial pressure catalysis reaction more described than step (1).
8. according to the method for claim 1, it is characterised in that the catalyst 2 described in step (5) is that HZSM-5 and HY is compound
The HZSM-5 that molecular sieve catalyst, preferably phosphorus and tungsten are modified and HY composite molecular sieve catalysts, the mass content of wherein phosphorus are
The mass content of 1.5%-7.0%, tungsten are 0.3%-2.0%；The usage amount of catalyst 2 is that catalysis reaction is added in step (5)
The 5%-20% of reaction mass gross mass, preferably 10%-15% added by whole in device C.
9. according to the method described in claim 1 or 8, it is characterised in that the preparation method of the catalyst 2 described in step (5) is：
HZSM-5 and HY is with mass ratio 0.5-2:1 carries out being mixed to get composite molecular screen, and the phosphoric acid for being 10%-20% with mass concentration is molten
The mass ratio of liquid dipping composite molecular screen, phosphoric acid solution and composite molecular screen is 0.5-1:1, dry 1-3 is small at 80-110 DEG C
When, then with mass concentration be 1%-2% sodium tungstate solution impregnate composite molecular screen, the matter of sodium tungstate solution and composite molecular screen
Amount is than being 0.5-1:1, it is 5-10 hours dry at 80-110 DEG C, then roasted 4-7 hours at 330-380 DEG C, after molding
To catalyst 2.
10. according to the method for claim 1, it is characterised in that the reaction item of step (5) the Deep catalytic cracking reaction
Part is：Reaction temperature is 400-700 DEG C, preferably 500-600 DEG C；Reaction time is 60-150 minutes；Reaction under stiring into
Row, stir speed (S.S.) are 350-600 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 5-10MPa, further, it is preferable to
Reaction condition it is as follows：The reaction temperature of the reaction temperature catalysis reaction more described than step (3) of step (5) the catalysis reaction is extremely
It is few 50 DEG C high, at least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure catalysis reaction more described than step (3) of step (5) the catalysis reaction.
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| CN114434685A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Leaching device and application thereof, and device and method for recycling waste plastics containing PVC (polyvinyl chloride) |
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| 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 |
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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 |
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| CN114434685A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Leaching device and application thereof, and device and method for recycling waste plastics containing PVC (polyvinyl chloride) |
| CN114434685B (en) * | 2020-10-30 | 2023-08-08 | 中国石油化工股份有限公司 | Leacher and application thereof, device for recycling waste plastics containing PVC and method thereof |
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