CN108239552B - A kind of method for the treatment of of waste plastics and cellulose - Google Patents
A kind of method for the treatment of of waste plastics and cellulose Download PDFInfo
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- 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
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- 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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
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- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/14—Hydrocarbons
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- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/16—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of methods for the treatment of of waste plastics and cellulose.This method comprises: waste plastics carries out catalytic pyrolysis under the catalytic action of modified HY zeolite catalyst, resulting product 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, product liquid II 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 IV, product liquid iv and insoluble matter I and insoluble matter i carries out Deep catalytic cracking reaction, products therefrom is separated through gas-liquid-solid, isolated product liquid V is respectively through tetrahydrofuran and thiacyclohexane extraction and separation, 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, in particular to the method for a kind for the treatment of of waste plastics and cellulose.
Background technique
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 lower, is difficult 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 use 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 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.
Summary of the invention
Aiming at the deficiencies in the prior art, the present invention provides a kind of methods for the treatment of of 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 liquid yield, improves the economic benefit and environmental benefit of entire technique.
A kind of method for the treatment of of waste plastics and cellulose provided by the invention, comprising the following steps:
(1) waste plastics is added in catalytic reactor A, carries out catalytic cracking reaction, gained under the action of catalyst 1
Pyrolysis product be isolated to product liquid I, gas I and insoluble matter I；
(2) the resulting product liquid I of step (1) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted,
Respectively obtain the tetrahydrofuran solution of the II containing product liquid, the cyclohexane solution of the III containing product liquid and remaining product liquid
IV；
(3) tetrahydrofuran solution of the II containing product liquid obtained to step (2) and the hexamethylene of the III containing product liquid are molten
Liquid carries out distillation respectively and handles to remove solvent, the product liquid II and product liquid III that respectively obtain；
(4) cellulose and step (3) resulting product liquid II are added in catalytic reactor B, in the effect of catalyst 2
Under carry out catalysis reaction, be isolated to product liquid i, gas i and insoluble matter i；
(5) by the resulting product liquid i of step (4) is successively passed through tetrahydrofuran 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 remaining liquid and produce
Object iv obtains product liquid ii and product liquid iii by distillation processing to remove solvent；
(6) remaining product liquid IV, remaining product liquid iv and the step that step (2) and step (5) are respectively obtained
Suddenly the insoluble matter I and insoluble matter i that (1) and step (4) respectively obtain are added in catalytic reactor C, under the action of catalyst 3
Deep catalytic cracking reaction is carried out, resulting pyrolysis product is isolated to product liquid V, gas V and insoluble matter V；
(7) by the resulting product liquid V of step (6) is successively passed through tetrahydrofuran 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 remaining liquid and produce
Object VIII obtains product liquid VI and product liquid VII by distillation processing to remove solvent；
Wherein, catalyst 1 described in step (1) is Sn and P modified HY zeolite catalyst.
In the present invention, described catalytic reactor A, B and C are slurry bed system catalytic cracking reaction device.
In the present invention, waste plastics described in step (1) mainly includes 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, the usage amount of catalyst 1 described in step (1) is the 5%-20%, preferably 10%- of added waste plastics gross mass
15%.
In the present invention, in catalyst 1 described in step (1), the mass content of modifying agent Sn and P are 1%-12%, preferably
For 3%-10%.Wherein the molar ratio of Sn and P is 2-6:1, preferably 2-4:1.
In the present invention, Sn and P modified HY zeolite catalyst can be modified using the method for modifying of this field routine
And it obtains, such as ion-exchange, infusion process etc..
In the present invention, the reaction condition of 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, cooling described in step (2), step (5) and step (7) is preferably by product liquid I, liquid
Body product cold i and product liquid V are but to room temperature.
In the present invention, distillation processing described in step (3), step (5) and step (7) is the distillation side of this field routine
Method, to remove tetrahydrofuran or thiacyclohexane solvent.
In the present invention, cellulose described in step (4) is one of plant fibers substances such as stalk, bark, straw
Or it is several.
In the present invention, cellulose described in step (4) 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, and the processing time is 60-120
Minute.
In the present invention, step (3) resulting product liquid II, cellulose and product liquid II mass are added in step (4)
Than for 0.8-1.2:1.
In the present invention, catalyst 2 described in step (4) is mixing one or two kinds of in iron naphthenate and molybdenum naphthenate
Object, the preferably mixture of the two.The usage amount of the catalyst 2 is calculated as 800-1200ppm with the gross mass content of iron and molybdenum.
Sulphur source that mass content is calculated as 4000-8000ppm using sulphur is added while catalyst 2 are added in step (4) as vulcanizing agent, makes to urge
Changing the mass ratio of sulfur content and iron and molybdenum total content in reactor B is 5-7:1, wherein selected sulphur source be sulphur, hydrogen sulfide,
One of carbon disulfide etc. is a variety of.
In the present invention, the reaction condition of catalysis reaction described in step (4) 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 stirring rate 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: step (4) it is described catalysis reaction reaction temperature 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 (4) the catalysis reaction is anti-
At least high 2MPa of the hydrogen partial pressure answered.
In the present invention, catalyst 3 described in step (6) is HZSM-5 and HY composite molecular sieve catalyst, HZSM-5 with
The mass ratio 0.5-2:1 of HY, preferably phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst, wherein the quality of phosphorus contains
Amount is 1.5%-7.0%, and the mass content of tungsten is 0.3%-2.0%.The usage amount of the catalyst 3 is to be added in step (6)
The 5%-15% of reaction mass gross mass, preferably 6%-11% added by whole in catalytic reactor C.
In the present invention, the preparation method of used catalyst 3 is preferably as follows: HZSM-5 and HY carry out being mixed to get compound molecule
Sieve impregnates composite molecular screen with the phosphoric acid solution that mass concentration is 10%-20%, 1-3 hours dry at 80-110 DEG C；Use matter
The wolframic acid sodium water solution that amount concentration is 1%-2% impregnates composite molecular screen again, 5-10 hours dry at 80-110 DEG C, finally
It is roasted 4-7 hours at 330-380 DEG C, catalyst 3 is obtained after molding.
In the present invention, the catalyst 3 can be formed using conventional method, such as compression molding etc., in forming process
It can according to need addition shaping assistant.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 3.The phosphorus and tungsten modified HZSM-5 and HY composite molecular screen is catalyzed
In agent phosphorus there may be form be one of phosphotungstic acid, the oxide of phosphorus, phosphotungstate, phosphoric acid, phosphate etc. or it is a variety of,
Tungsten there may be form be one of phosphotungstic acid, the oxide of tungsten, phosphotungstate etc. or it is a variety of, it is preferred to use the above method
The catalyst of preparation.
In the present invention, the reaction condition of step (6) the Deep catalytic cracking reaction are as follows: reaction temperature is 400-700 DEG C,
Preferably 500-600 DEG C；Reaction time is 60-150 minutes；Reaction carries out under stiring, and stirring rate 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 (6) institute
The reaction temperature for stating the reaction temperature catalysis reaction more described than step (4) of catalysis reaction is at least 50 DEG C high, step (6) described catalysis
At least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure of the reaction catalysis reaction more described than step (4).
Compared with prior art, the invention has the following advantages that
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 combines, 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 improve the yield of hexamethylene soluble matter and tetrahydrofuran soluble matter.
Catalyst of the modified HY zeolite as waste plastics catalytic pyrolysis for selecting Sn and P, make waste plastics selectivity with higher with
Conversion ratio is conducive to the liquid yield for improving entire technique.The liquid being obtained by extraction after waste plastics catalytic pyrolysis by tetrahydrofuran
Product is pyrolyzed jointly with cellulose, and the dissolution for helping to improve polarity in cellulose catalytic reaction process improves cellulose
Conversion ratio.In addition, the insoluble matter of waste plastics and cellulose after catalysis reaction is collected mixing by the present invention, and be added waste plastics and
The remaining liq product not extracted by tetrahydrofuran and hexamethylene after cellulose catalytic reaction carries out under the effect of the catalyst
Deep catalytic cracking reaction reduces the generation of a large amount of waste residues.For waste residue difficult to deal with, especially with phosphorus of the invention and
Tungsten modified HZSM-5 and HY composite molecular sieve catalyst, cracking temperature is more mild, and cleavage rate is high.
In addition, present invention process process is simple, reaction condition is mild, simple and easy, 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.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention；
The reference numerals are as follows: 1, catalytic reactor A；2, gas-liquid-solid separator a；3, be successively arranged 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 successively arranged with tetrahydrofuran
It is the extraction equipment b of solvent with hexamethylene；7, catalytic reactor C；8, gas-solid separating device c；9, it is successively arranged with tetrahydrofuran
It is the extraction equipment c of solvent with hexamethylene；21, liquid product I；22, gas I；23 insoluble matter I；31, product liquid II, 32, liquid
Body product III；33, remaining product liquid IV；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, insoluble matter V；91, liquid produces
Object VI；92, product liquid VII；93, remaining product liquid VIII.
Specific embodiment
Further illustrate processing method of the invention below with reference to specific embodiment, but protection scope of the present invention
And it is not so limited to the range of following embodiment.Wherein in the present invention, wt% representation quality score.
As shown in Figure 1, the method for the treatment of of waste plastics provided by the invention and cellulose, comprising the following steps:
(1) waste plastics is added in catalytic reactor A 1, 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 resulting product liquid I 21 of step (1), which is successively passed through to be equipped with tetrahydrofuran and hexamethylene after cooling, is
The extraction equipment a 3 of solvent is extracted, and the tetrahydrofuran solution of the II containing product liquid, the III containing product liquid are respectively obtained
Cyclohexane solution and remaining product liquid IV 33；
(3) tetrahydrofuran solution of the II containing product liquid obtained to step (2) and the hexamethylene of the III containing product liquid are molten
Liquid carries out distillation respectively and handles to remove solvent, the product liquid II 31 and product liquid III 32 that respectively obtain；
(4) cellulose is charged first in catalytic reactor B 4 and is carried out dehydrating, then added obtained by step (3)
Product liquid II 31, carry out catalysis reaction under the action of catalyst 2, through the isolated liquid of gas-liquid-solid separator b 5 produce
Object i 51, gas i 52 and insoluble matter i 53；
(5) the resulting product liquid i 51 of step (4) is successively passed through after cooling and is 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 distillation processing to remove solvent, obtain 61 He of product liquid ii
Product liquid iii 62；
(6) remaining product liquid IV 33, the remaining product liquid iv that step (2) and step (5) are respectively obtained
63 and step (1) and step (4) 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 3, resulting pyrolysis product is isolated through gas-liquid solid separation device c 8
Product liquid V 81, gas V 82 and insoluble matter V 83；
(7) the resulting product liquid V81 of step (6) is passed through to be successively arranged after cooling and is with tetrahydrofuran and hexamethylene
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 He of product liquid VI by distillation 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 32, product liquid iii 62 and product liquid
VII 92, tetrahydrofuran soluble matter are product liquid ii 61 and product liquid VI 91, and residue is insoluble matter V 83 and residue
Product liquid VIII 93.Conversion ratio refers to that gas in product, hexamethylene soluble matter, tetrahydrofuran soluble matter gross mass account for
The percentage of four kinds of product qualities.In the present invention, gas is mainly the low-carbon alkene below of the carbon such as ethylene and propylene four.
Catalyst 1 is modified HY molecular sieve using dipping method to obtain modified HY points of Sn and P in the embodiment of the present invention
Sub- sieve catalyst.
Catalyst 1-A is Sn and P modified HY zeolite catalyst in the embodiment of the present invention, the matter of Sn and P in the catalyst
Measuring content is 5%, and wherein the molar ratio of Sn and P is 3:1.
Catalyst 1-B is Sn and P modified HY zeolite catalyst in the embodiment of the present invention, the matter of Sn and P in the catalyst
Measuring content is 8%, and wherein the molar ratio of Sn and P is 2.5:1.
Catalyst used in comparative example of the present invention is non-modified HY molecular sieve catalyst.
Phosphorus used in the embodiment of the present invention and tungsten modified HZSM-5 and HY composite molecular sieve catalyst CAT-A are specifically such as
Under: the mass ratio of HZSM-5 and HY composite molecular screen is 1:1, and the mass content of phosphorus is 3%, and the mass content of tungsten is 1.2%,
The preparation method is as follows: HZSM-5 is mixed with HY molecular sieve, compound molecule is impregnated with the phosphoric acid solution that mass concentration is 15%
Sieve, it is 2 hours dry at 100 DEG C；Composite molecular screen is impregnated with the wolframic acid sodium water solution that mass concentration is 1.5%, at 100 DEG C
It is 8 hours dry, it is finally roasted 6 hours at 350 DEG C, through compression molding, sieving, taking granular size is the solid of 40 mesh to 60 mesh
The particle HZSM-5 and HY composite molecular sieve catalyst CAT-A modified as phosphorus and tungsten.
HZSM-5 used in the embodiment of the present invention and HY composite molecular sieve catalyst CAT-B is specific as follows: HZSM-5 and HY
The mass ratio of composite molecular screen is 1:1, and preparation method is as follows: HZSM-5 is mixed with HY 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, taking granular size is the solid of 40 mesh to 60 mesh
Particle is as HZSM-5 and HY composite molecular sieve catalyst 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, catalytic pyrolysis carried out under the catalytic action of catalyst 1-A
Reaction, catalyst 1-A additive amount are the 12% of waste plastics gross mass, and the reaction condition of catalytic cracking reaction is as follows: reaction temperature
It is 460 DEG C, the reaction time is 60 minutes, and stirring rate is 430 revs/min, needs to be passed through hydrogen into catalytic reactor A in reaction
Gas, hydrogen partial pressure 2.9MPa separate the product after reaction, obtain product liquid I, gas I and insoluble matter I；By liquid
Product I is cooled to after room temperature and is successively passed through tetrahydrofuran, cyclohexane solvent is extracted, and respectively obtains the II's containing product liquid
The cyclohexane solution and remaining liquid product IV of tetrahydrofuran solution, the III containing product liquid；To obtained II containing product liquid
Tetrahydrofuran solution and the cyclohexane solution of the III containing product liquid carry out distillation processing to remove solvent, obtained liquid produces
Object II and product liquid III；2g stalk is crushed to the powder that length is about 10mm, is then carried out at dehydration under anaerobic
Reason, treatment temperature are 130 DEG C, and the processing time is 70 minutes, and the stalk after pre-processing is added to slurry bed system catalytic cracking reaction
In device B, the iron naphthenate and molybdenum naphthenate that each 500ppm of mass content is then added into slurry bed system catalytic cracking reaction device B are made
For catalyst, while sulphur that mass content is 6000ppm is added as vulcanizing agent, makes sulfur content in catalytic pyrolysis catalyst converter B
It is 6:1 with the mass ratio of iron and molybdenum total content, and product liquid II is passed through slurry bed system catalytic cracking reaction device B, then such as
Reacted under lower reaction condition: reaction temperature is 515 DEG C, and the reaction time is 80 minutes, and stirring rate is 450 revs/min, instead
The needs answered are passed through hydrogen into slurry bed system catalytic cracking reaction device B, and hydrogen partial pressure 5.6MPa carries out the product after reaction
Separation, obtains product liquid i, gas i and insoluble matter i；Tetrahydro furan is successively passed through after resulting liquid product i is cooled to room temperature
It mutters and is extracted with cyclohexane solvent, obtain the tetrahydrofuran solution of the ii containing product liquid and the hexamethylene of the iii containing product liquid
Solution and remaining product liquid iv, and the hexamethylene of the tetrahydrofuran solution to the ii containing product liquid and the iii containing product liquid
Solution carries out distillation processing to remove solvent, obtains product liquid ii and product liquid iii.
Remaining product liquid IV, remaining product liquid iv and insoluble matter I and insoluble matter i are added to slurry bed system catalysis
Deep catalytic cracking reaction is carried out in cracking reactor C, the HZSM-5 and HY that the phosphorus in the above way prepared and tungsten are modified is compound
For molecular sieve as catalyst CAT-A, the usage amount of the catalyst is all reactions being added in slurry bed system catalytic cracking reaction device C
The 11% of material gross mass, Deep catalytic cracking reaction is carried out under following reaction condition: reaction temperature is 590 DEG C, when reaction
Between be 100 minutes, 440 revs/min of stirring rate, the needs in reaction are passed through hydrogen into slurry bed system catalytic cracking reaction device C,
Its hydrogen partial pressure is 8.0MPa, and resulting pyrolysis product is isolated to product liquid V, gas V and insoluble matter V；By resulting liquid
Body product V is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted, and respectively obtains the tetrahydro of the VI containing product liquid
The cyclohexane solution and remaining product liquid VIII of tetrahydrofuran solution, the VII containing product liquid, it is molten to remove by distillation processing
Agent obtains product liquid VI and product liquid VII.
Embodiment 2
The reaction condition of the catalytic cracking reaction carried out in slurry bed system catalytic cracking reaction device A will be only urged in embodiment 1
Be changed to: reaction temperature is 450 DEG C, and the reaction time is 100 minutes, and stirring rate is 480 revs/min, is needed in reaction to slurry
Hydrogen is passed through in bed catalytic cracking reaction device A, hydrogen partial pressure 3.2MPa, slurry bed system catalytic cracking reaction device C carry out Deep catalytic
The condition of cracking reaction is changed to: reaction temperature is 570 DEG C, and the reaction time is 110 minutes, 500 revs/min of stirring rate, is reacted
In needs be passed through hydrogen, hydrogen partial pressure 6.6Pa into slurry bed system catalytic cracking reaction device C.
Embodiment 3
The iron naphthenate of each 500ppm of mass content in embodiment 1 and molybdenum naphthenate are only revised as mass content
The iron naphthenate of 1000ppm, and cellulose catalytic reaction condition is changed to: reaction temperature is 535 DEG C, hydrogen partial pressure 7.0MPa,
The other the same as in Example 1.
Embodiment 4
The iron naphthenate of each 500ppm in embodiment 1 and molybdenum naphthenate are only revised as to the molybdenum naphthenate of 1000ppm,
The other the same as in Example 1.
Embodiment 5
Change the catalyst CAT-A in embodiment 4 into CAT-B, the other the same as in Example 1.
Embodiment 6
Only change the catalyst 1-A in embodiment 1 into catalyst 1-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 2g stalk
It is added in slurry bed system catalytic cracking reaction device by the powder of length about 10mm jointly, urges in non-modified HY molecular sieve
Catalytic cracking reaction is carried out under the catalytic action of agent, the additive amount of HY molecular sieve is waste plastics and cellulose gross mass
12%, the reaction condition of catalytic cracking reaction is as follows: reaction temperature is 520 DEG C, and the reaction time is 70 minutes, and stirring rate is
It 430 revs/min, needs to be passed through hydrogen, hydrogen partial pressure 5.6MPa, after reaction into slurry bed system catalytic cracking reaction device in reaction
Product separated, obtain product liquid 1, gas and waste residue；Tetrahydro is successively passed through after product liquid 1 is cooled to room temperature
Furans, cyclohexane solvent are extracted, and the tetrahydrofuran solution containing product liquid 2, the hexamethylene containing product liquid 3 are respectively obtained
Solution and remaining liquid product IV, and to the tetrahydrofuran solution containing product liquid 2, the cyclohexane solution containing product liquid 3
It is distilled to remove solvent, obtains product liquid 2 and product liquid 3.
The distribution of 1 embodiment 1-6 of table and 1 products therefrom of comparative example and conversion ratio comparison
| Number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Product distribution, wt% | |||||||
| Gas | 3.3 | 5.6 | 8.5 | 9.3 | 12.9 | 4.1 | 13.5 |
| Hexamethylene soluble matter | 32.2 | 35.4 | 34.2 | 34.0 | 28.1 | 37.9 | 19.8 |
| Tetrahydrofuran soluble matter | 58.6 | 51.2 | 44.6 | 43.4 | 36.1 | 51.4 | 24.2 |
| Residue | 5.9 | 7.8 | 12.7 | 13.3 | 22.9 | 6.6 | 42.5 |
| Conversion ratio, wt% | 94.1 | 92.2 | 87.3 | 86.7 | 77.1 | 93.4 | 57.5 |
Claims (20)
1. a kind for the treatment of of waste plastics and cellulose method, comprising the following steps:
(1) waste plastics is added in catalytic reactor A, catalytic cracking reaction is carried out under the action of catalyst 1, it is resulting to split
Solution product is isolated to product liquid I, gas I and insoluble matter I；
(2) the resulting product liquid I of step (1) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted, respectively
Obtain the tetrahydrofuran solution of the II containing product liquid, the cyclohexane solution of the III containing product liquid and remaining product liquid IV；
(3) cyclohexane solution of the tetrahydrofuran solution for the II containing product liquid that step (2) is obtained and the III containing product liquid point
It does not carry out distillation to handle to remove solvent, the product liquid II and product liquid III that respectively obtain；
(4) cellulose and step (3) resulting product liquid II are added in catalytic reactor B, under the action of catalyst 2 into
Row catalysis reaction, is isolated to product liquid i, gas i and insoluble matter i；
(5) by the resulting product liquid i of step (4) is successively passed through tetrahydrofuran 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 distillation processing to remove solvent, product liquid ii and product liquid iii are obtained；
(6) remaining product liquid IV, remaining product liquid iv and the step (1) that step (2) and step (5) are respectively obtained
The insoluble matter I and insoluble matter i respectively obtained with step (4) is added in catalytic reactor C, is carried out under the action of catalyst 3
Deep catalytic cracking reaction, resulting pyrolysis product are isolated to product liquid V, gas V and insoluble matter V；
(7) by the resulting product liquid V of step (6) is successively passed through tetrahydrofuran 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 distillation processing to remove solvent；
Wherein, catalyst 1 described in step (1) is Sn and P modified HY zeolite catalyst；Catalyst 2 described in step (4) is
One or two kinds of mixture in iron naphthenate and molybdenum naphthenate；Catalyst 3 described in step (6) is that HZSM-5 and HY is compound
Molecular sieve catalyst.
2. according to the method for claim 1, it is characterised in that waste plastics described in step (1) includes vinyon, gathers
The mixture of one or more of Acrylic plastic, polystyrene, 80% of total content not less than addition waste plastics gross mass.
3. according to the method for claim 1, it is characterised in that the usage amount of the catalyst 1 is the total matter of added waste plastics
The 5%-20% of amount；The mass content of Sn and P is 1%-12% in Sn the and P modified HY zeolite catalyst, wherein Sn
Molar ratio with P is 2-6:1.
4. according to the method for claim 3, it is characterised in that the usage amount of the catalyst 1 is the total matter of added waste plastics
The 10%-15% of amount.
5. according to the method for claim 3, it is characterised in that Sn and P in Sn the and P modified HY zeolite catalyst
Mass content be 3%-10%, wherein the molar ratio of Sn and P be 2-4:1.
6. according to the method for claim 1, it is characterised in that the reaction condition of catalytic cracking reaction described in step (1) is such as
Under: reaction temperature is 350-550 DEG C, and the reaction time is 30-150 minutes, and reaction carries out under stiring, stirring rate 350-
600 revs/min, need to be passed through hydrogen, hydrogen partial pressure 2-4MPa in reaction.
7. according to the method for claim 6, it is characterised in that the reaction condition of catalytic cracking reaction described in step (1) is such as
Under: reaction temperature is 400-480 DEG C, and the reaction time is 45-120 minutes, and reaction carries out under stiring, stirring rate 400-
500 revs/min, need to be passed through hydrogen, hydrogen partial pressure 2.5-3.5MPa in reaction.
8. according to the method for claim 1, it is characterised in that cellulose described in step (4) is stalk, one in bark
Kind or two kinds；The cellulose is added to before catalytic reactor B, is first pre-processed, it is described pretreatment include pulverization process,
At least one of dehydration, of length no more than 20mm of cellulose substances after pulverization process, the dehydration is in nothing
It is carried out under the conditions of oxygen, treatment temperature is 100-200 DEG C, and the processing time is 60-120 minutes.
9. according to the method for claim 1, it is characterised in that catalyst 2 described in step (4) is iron naphthenate and cycloalkanes
The mixture of sour molybdenum.
10. according to method described in claim 1 or 9, it is characterised in that the usage amount of catalyst 2 described in step (4) is with iron
800-1200ppm is calculated as with the gross mass content of molybdenum；Mass content is added while catalyst 2 are added in step (4) to be calculated as with sulphur
The sulphur source of 4000-8000ppm is as vulcanizing agent, and the mass ratio of sulfur content and iron and molybdenum total content is 5-7 in catalytic reactor B:
1, selected sulphur source are as follows: one of sulphur, hydrogen sulfide, carbon disulfide are a variety of.
11. according to the method for claim 1, it is characterised in that the reaction condition of catalysis reaction described in step (4) is as follows:
Reaction temperature is 400-600 DEG C, and the reaction time is 30-100 minutes, and reaction carries out under stiring, stirring rate 350-600
Rev/min, need to be passed through hydrogen, hydrogen partial pressure 4-8MPa in reaction.
12. according to the method for claim 11, it is characterised in that the reaction condition of catalysis reaction described in step (4) is such as
Under: reaction temperature is 450-550 DEG C, and the reaction time is 60-100 minutes, and reaction carries out under stiring, stirring rate 400-
500 revs/min, need to be passed through hydrogen, hydrogen partial pressure 5-6.5MPa in reaction.
13. according to method described in claim 11 or 12, it is characterised in that the reaction temperature ratio of step (4) the catalysis reaction
The reaction temperature of step (1) described catalytic cracking reaction is at least 50 DEG C high, and the hydrogen partial pressure of step (4) the catalysis reaction compares step
(1) at least high 2MPa of the hydrogen partial pressure of the catalytic cracking reaction.
14. according to the method for claim 1, it is characterised in that catalyst 3 described in step (6) is that phosphorus and tungsten are 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%.
15. according to method described in claim 1 or 14, it is characterised in that the usage amount of catalyst 3 described in step (6) is step
Suddenly the 5%-15% of reaction mass gross mass added by the whole in catalytic reactor C is added in (6).
16. according to the method for claim 15, it is characterised in that it is characterized in that catalyst 3 described in step (6) makes
Dosage is that reaction mass gross mass added by the middle whole being added in catalytic reactor C of step (6) is 6%-11%.
17. according to the method for claim 14, it is characterised in that catalyst 3 described in step (6) the preparation method comprises the following steps:
HZSM-5 and HY carries out being mixed to get composite molecular screen with mass ratio 0.5-2:1, 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, and dry 1-3 is small at 80-110 DEG C
When, then the sodium tungstate solution dipping composite molecular screen for being 1%-2% with mass concentration, the matter of sodium tungstate solution and composite molecular screen
Amount is 5-10 hours dry at 80-110 DEG C than being 0.5-1:1, then roasts 4-7 hours at 330-380 DEG C, after molding
To catalyst 3.
18. according to the method for claim 1, it is characterised in that the reaction item of step (6) the Deep catalytic cracking reaction
Part are as follows: reaction temperature is 400-700 DEG C；Reaction time is 60-150 minutes；Reaction carries out under stiring, stirring rate 350-
600 revs/min；Need to be passed through hydrogen, hydrogen partial pressure 5-10MPa in reaction.
19. according to the method for claim 18, it is characterised in that the reaction item of step (6) the Deep catalytic cracking reaction
Part are as follows: reaction temperature is 500-600 DEG C.
20. according to method described in claim 18 or 19, it is characterised in that step step (6) the Deep catalytic cracking reaction
The reaction temperature catalysis reaction more described than step (4) reaction temperature it is at least 50 DEG C high, step (6) Deep catalytic cracking is anti-
At least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure the answered catalysis reaction more described than step (4).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06220461A (en) * | 1993-01-22 | 1994-08-09 | Mazda Motor Corp | Production of hydrocarbon oil from waste plastic or rubber material and equipment for use therein |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
| CN103484142A (en) * | 2013-09-25 | 2014-01-01 | 清华大学 | Method for preparing aromatic hydrocarbon through co-catalytic pyrolysis of biomass and plastic |
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| PL2348091T3 (en) * | 2010-01-12 | 2013-04-30 | Ifp Energies Now | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06220461A (en) * | 1993-01-22 | 1994-08-09 | Mazda Motor Corp | Production of hydrocarbon oil from waste plastic or rubber material and equipment for use therein |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
| CN103484142A (en) * | 2013-09-25 | 2014-01-01 | 清华大学 | Method for preparing aromatic hydrocarbon through co-catalytic pyrolysis of biomass and plastic |
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