CN108117882B - A method of processing waste plastics and cellulose - Google Patents
A method of processing waste plastics and cellulose Download PDFInfo
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- CN108117882B CN108117882B CN201810142808.1A CN201810142808A CN108117882B CN 108117882 B CN108117882 B CN 108117882B CN 201810142808 A CN201810142808 A CN 201810142808A CN 108117882 B CN108117882 B CN 108117882B
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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
-
- 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
- C10G1/086—Characterised by the catalyst used
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- 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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- 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
- C10G2300/1011—Biomass
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of methods for processing waste plastics and cellulose.This method comprises: waste plastics is through the resulting product of 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 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, 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, in particular to a kind of method for processing 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 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.
A kind of method for processing 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 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 cellulose and step (2) resulting II containing product liquid
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 resulting product liquid i of step (3) 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；
(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, resulting pyrolysis product is isolated to product liquid V, gas V and insoluble matter V；
(6) by the resulting product liquid V of step (5) 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, described in step (1)
Catalyst agent 1 is made of two kinds of catalyst, and one is the catalysis of kaolin and montmorillonite load iron naphthenate and/or molybdenum naphthenate
Agent, secondly being HY molecular sieve 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, kaolin and montmorillonite load iron naphthenate and/or aphthenic acids in catalyst 1 described in step (1)
The mass ratio of molybdenum catalyst and HY molecular sieve catalyst is 0.14-3:1, preferably 0.2-0.7:1.
In the present invention, kaolin and montmorillonite load iron naphthenate and/or aphthenic acids in catalyst 1 described in step (1)
In molybdenum catalyst, by weight, the weight ratio of kaolin and montmorillonite is 2.5-1:1, and kaolin and montmorillonite account for 37.5%-
87.5%, iron naphthenate and/or molybdenum naphthenate account for 12.5%-62.5%, and the preferably weight ratio of kaolin and montmorillonite is 2-
1:1, kaolin and montmorillonite account for 50%-70%, and molybdenum naphthenate and/or iron naphthenate account for 30%-50%.
In the present invention, kaolin and montmorillonite load iron naphthenate and/or aphthenic acids in catalyst 1 described in step (1)
Molybdenum catalyst the preparation method is as follows:
1) kaolin and montmorillonite roast 2-10h after 400-550 DEG C, and the heating rate for being preferably warming up to maturing temperature is
5-10℃/min；
2) kaolin obtained after step 1) roasting and montmorillonite are added in reactor, ring is then added into reactor
The diluted acid maceration extract of alkanoic acid iron and/or molybdenum naphthenate is impregnated, and dipping while is preferably stirred, stirring rate 100-
150r/min, mixing time 0.5-2.5h；
3) by the material after step 2) reaction, dry 2-6h, obtained kaolin and montmorillonite are negative under the conditions of 100-150 DEG C
Carry iron naphthenate and/or molybdenum naphthenate catalyst.
The preparation method of the kaolin and montmorillonite load iron naphthenate and/or molybdenum naphthenate catalyst, step 2)
Described in diluted acid be at least one of hydrochloric acid, nitric acid and acetic acid, the mass concentration of diluted acid maceration extract is 5%-20%.It is described
Maceration extract can use organic solution, preferred alcohol solution.The dipping uses conventional impregnation method, such as saturation infusion process
Or supersaturated infusion process.
Kaolin and montmorillonite load iron naphthenate of the invention and/or molybdenum naphthenate catalyst can use conventional method
Molding, such as compression molding etc., can according to need addition shaping assistant in forming process.It, can be by step (3) in the present invention
Resulting material is formed after drying, to obtain molding catalytic cracking catalyst.After compression molding, as needed into
Row sieving, taking granular size is 30 mesh to 70 mesh, preferably 40 to 60 mesh.
In the present invention, the usage amount of catalyst 1 described in step (1) is the 5%-20% of added waste plastics gross mass, excellent
It is selected as 10%-15%.
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, the mass ratio 1-3 of tetrahydrofuran described in step (2) and hexamethylene mixed solvent and product liquid I:
1, wherein the mass ratio of tetrahydrofuran and hexamethylene is 1-3:1, preferably 1-2:1.
In the present invention, 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, 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, cellulose described in step (3) is one of plant fibers substances such as stalk, bark, straw
Or it is several.
In the present invention, 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, and the processing time is 60-120
Minute.
In the present invention, tetrahydrofuran and the hexamethylene mixing of step (2) resulting II containing product liquid are added in step (3)
The tetrahydrofuran solution and hexamethylene mixed solvent mass ratio of solvent, cellulose and the II containing product liquid are 0.8-1.2:1.
In the present invention, step (3), which can according to need a certain amount of iron naphthenate of addition and/or molybdenum naphthenate, satisfaction, to be made
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)
The sulphur source that content is calculated as 4000-8000ppm using sulphur makes sulfur content and iron and molybdenum total content in catalytic reactor B as vulcanizing agent
Mass ratio be 5-7:1, wherein selected sulphur source is one of sulphur, hydrogen sulfide, carbon disulfide etc. or a variety of.
In the present invention, the reaction condition of 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 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 (3) 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 (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 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 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 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；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, the catalyst 2 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 2.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 (5) 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 (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 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.
Especially waste plastics catalytic pyrolysis is made using kaolin and montmorillonite load iron naphthenate and/or molybdenum naphthenate, HY molecular sieve
For catalyst, after be pyrolyzed jointly by the product liquid that tetrahydrofuran and hexamethylene mixed solution are obtained by extraction with cellulose, wherein
The use of kaolin and montmorillonite load iron naphthenate and/or molybdenum naphthenate catalyst not only facilitates the cracking for improving plastics
Rate, and the dissolution of polarity and catalyzed conversion in cellulose catalytic reaction process are also promoted, improve turning for cellulose
Rate.In addition, the insoluble matter of waste plastics and cellulose after catalysis reaction is collected mixing by the present invention, and waste plastics and fibre is added
The remaining liq product not extracted by tetrahydrofuran and hexamethylene after dimension element catalysis reaction carries out deep under the effect of the catalyst
Catalytic cracking reaction is spent, the generation of a large amount of waste residues is reduced.For waste residue difficult to deal with, especially with phosphorus and tungsten of the invention
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, 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 embodiment
Further illustrate preparation 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.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 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 resulting product liquid I 21 of 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, separated through gas-liquid-solid
The isolated product liquid i 51 of device b 5, gas i 52 and insoluble matter i 53；
(4) the resulting product liquid i 51 of step (3) 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；
(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, 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；
(6) the resulting product liquid V81 of step (5) 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 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 the low-carbon alkene below of the carbon such as ethylene and propylene four.
Catalyst 1-A used in the embodiment of the present invention: with the poidometer of catalyst, kaolin and montmorillonite load aphthenic acids
The mass ratio of iron and molybdenum naphthenate catalyst and HY molecular sieve catalyst is 0.32:1, kaolin and montmorillonite load iron naphthenate
In molybdenum naphthenate catalyst, by weight, kaolin and montmorillonite account for 60%, and the weight ratio of kaolin and montmorillonite is 2:1,
Iron naphthenate account for 20% and molybdenum naphthenate account for 20%.
Catalyst 1-B used in the embodiment of the present invention: with the poidometer of catalyst, kaolin and montmorillonite load aphthenic acids
The mass ratio of iron and molybdenum naphthenate catalyst and HY molecular sieve catalyst is 0.4:1, kaolin and montmorillonite load iron naphthenate
In molybdenum naphthenate catalyst, by weight, kaolin and montmorillonite account for 55%, and the weight ratio of kaolin and montmorillonite is 1.5:
1, iron naphthenate account for 15% and molybdenum naphthenate account for 20%.
Wherein kaolin and montmorillonite load iron naphthenate and molybdenum naphthenate catalyst the preparation method is as follows: 1) by kaolinite
Soil and montmorillonite original are in 480 DEG C of roasting 6h, wherein the rate for being warming up to maturing temperature is 7 DEG C/min；It 2) will be after step 1) roasting
Obtained kaolin and montmorillonite are added in reaction vessel, and the dilute of iron naphthenate and molybdenum naphthenate is then added into reaction vessel
The maceration extract of hydrochloric acid carries out supersaturated dipping, and maceration extract dosage is 1.2 times of saturation absorption water theory dosage, and maceration extract is ethyl alcohol
Solution, wherein the mass fraction of hydrochloric acid is 12%, is stirred, stirring rate 130r/min, mixing time 1.0h；3) by step
2) dry 3h under the conditions of 125 DEG C of the material after reaction, then through compression molding, sieving, taking granular size is 40 mesh to 60 purposes
Solid particle is as 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, 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 is 455 DEG C, the reaction time is 60 minutes, and stirring rate is 440 revs/min, needs to be passed through hydrogen into catalytic reactor A in reaction
Gas, hydrogen partial pressure 2.8MPa separate 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 1.8:1, and wherein the mass ratio of tetrahydrofuran and hexamethylene is 2:1, are respectively obtained containing liquid
Tetrahydrofuran and hexamethylene mixed solvent, the remaining liquid product III of body product II；3g stalk, which is crushed to length, is about
The powder of 10mm, is then carried out dehydrating under anaerobic, and treatment temperature is 130 DEG C, and the 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 iron naphthenate and molybdenum naphthenate in slurry bed system catalytic cracking reaction device B altogether containing each 500ppm of mass content
Catalyst, while mass content is added, the sulphur of 6000ppm is calculated as vulcanizing agent using sulphur, keep the catalysis of slurry bed system catalytic pyrolysis anti-
Answering the mass ratio of sulfur content and iron and molybdenum total content in device B is 6:1, is then reacted under following reaction condition: reaction temperature
Degree is 515 DEG C, and the reaction time is 70 minutes, and stirring rate is 430 revs/min, and needs in reaction are to slurry bed system catalytic pyrolysis
Hydrogen is passed through in reactor B, hydrogen partial pressure 5.6MPa separates the product after reaction, obtain product liquid i, gas i and
Insoluble matter i；Tetrahydrofuran is successively passed through after resulting liquid product i is cooled to room temperature and cyclohexane solvent extracts, and is obtained
To the tetrahydrofuran solution of the ii containing product liquid and the cyclohexane solution of the iii containing product liquid and remaining product liquid iv, and
It is molten to remove that the cyclohexane solution of tetrahydrofuran solution to the ii containing product liquid and the iii containing product liquid carry out distillation processing
Agent obtains product liquid ii and product liquid 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 the phosphorus in the above way prepared and tungsten are modified are 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 stirring rate, the needs in reaction are passed through hydrogen into slurry bed system catalytic cracking reaction device C
Gas, hydrogen partial pressure 7.0MPa, resulting pyrolysis product are isolated to product liquid V, gas V and insoluble matter V；It will be resulting
Product liquid V is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted, and respectively obtains four of the VI containing product liquid
The cyclohexane solution and remaining product liquid VIII of hydrogen 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
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
Are as follows: reaction temperature is 460 DEG C, and the reaction time is 110 minutes, and stirring rate is 480 revs/min, is needed in reaction to slurry bed system
Hydrogen is passed through in catalytic cracking reaction device A, hydrogen partial pressure 3.6MPa, slurry bed system catalytic cracking reaction device C carry out Deep catalytic and split
Solution reaction condition be changed to: reaction temperature be 575 DEG C, the reaction time be 120 minutes, 500 revs/min of stirring rate, in reaction
Needs be passed through hydrogen, hydrogen partial pressure 7.4MPa into slurry bed system catalytic cracking reaction device C.
Embodiment 3
Only change the catalyst 1-A in embodiment 1 into catalyst 1-B, the other the same as in Example 1.
Embodiment 4
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 stalk
It is added in slurry bed system catalytic cracking reaction device, in the catalysis of HY molecular sieve catalyst by the powder of length about 10mm jointly
Effect is lower to carry out catalytic cracking reaction, and the additive amount of HY molecular sieve 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 stirring rate 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 separates the product after reaction,
Obtain product liquid 1, gas and waste residue；Product liquid 1 is cooled to after room temperature and is successively passed through tetrahydrofuran, cyclohexane solvent
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 1-4 of table and 1 products therefrom of comparative example and conversion ratio comparison
| Number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Product distribution, wt% | |||||
| Gas | 4.1 | 7.1 | 5.8 | 9.4 | 13.3 |
| Hexamethylene soluble matter | 34.2 | 36.0 | 34.7 | 27.9 | 19.6 |
| Tetrahydrofuran soluble matter | 50.3 | 47.6 | 46.5 | 37.8 | 23.4 |
| Residue | 11.4 | 9.3 | 13.0 | 24.9 | 43.7 |
| Conversion ratio, wt% | 88.6 | 90.7 | 87.0 | 75.1 | 56.3 |
Claims (18)
1. a kind of method for processing waste plastics and cellulose, 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 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 and hexamethylene mixed solvent of cellulose and step (2) resulting II containing product liquid 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 resulting product liquid i of step (3) 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；
(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
Row Deep catalytic cracking reaction, resulting pyrolysis product are isolated to product liquid V, gas V and insoluble matter V；
(6) by the resulting product liquid V of step (5) 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 made of two kinds of catalyst, and one is kaolin and montmorillonite load aphthenic acids
The catalyst of iron and/or molybdenum naphthenate, secondly being HY molecular sieve catalyst；Catalyst 2 described in step (5) is HZSM-5 and HY
Composite molecular sieve catalyst.
2. according to the method for claim 1, it is characterised in that kaolin and montmorillonite in catalyst 1 described in step (1)
The mass ratio for loading iron naphthenate and/or molybdenum naphthenate catalyst and HY molecular sieve catalyst is 0.14-3:1；The catalysis
The usage amount of agent 1 is the 5%-20% of added waste plastics gross mass.
3. according to the method for claim 2, it is characterised in that kaolin and montmorillonite in catalyst 1 described in step (1)
The mass ratio for loading iron naphthenate and/or molybdenum naphthenate catalyst and HY molecular sieve catalyst is 0.2-0.7:1；The catalysis
The usage amount of agent 1 is the 10%-15% of added waste plastics gross mass.
4. according to the method for claim 1, it is characterised in that kaolin and montmorillonite in catalyst 1 described in step (1)
It loads in iron naphthenate and/or molybdenum naphthenate catalyst, by weight, the weight ratio of kaolin and montmorillonite is 2.5-1:1, high
Ridge soil and montmorillonite account for 37.5%-87.5%, and iron naphthenate and/or molybdenum naphthenate account for 12.5%-62.5%.
5. according to the method for claim 4, it is characterised in that kaolin and montmorillonite in catalyst 1 described in step (1)
It loads in iron naphthenate and/or molybdenum naphthenate catalyst, by weight, the weight ratio of kaolin and montmorillonite is 2-1:1, kaolinite
Soil and montmorillonite account for 50%-70%, and molybdenum naphthenate and/or iron naphthenate account for 30%-50%.
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 in reaction, hydrogen partial pressure is 2.5-3.5 MPa.
8. according to the method for claim 1, it is characterised in that 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%；Cellulose described in step (3) is one or both of stalk, bark；The cellulose is added to catalytic reactor B
Before, it is first pre-processed, the pretreatment includes at least one of pulverization process, dehydration, fiber after pulverization process
Of length no more than 20mm of plain material, the dehydration carry out under anaerobic, and treatment temperature is 100-200 DEG C,
Handling the time is 60-120 minutes.
9. 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 are as follows: one of sulphur, hydrogen sulfide, carbon disulfide are a variety of.
10. according to the method for claim 1, it is characterised in that the reaction condition of catalysis reaction described in step (3) 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.
11. according to the method for claim 10, it is characterised in that the reaction condition of catalysis reaction described in step (3) 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 in reaction, hydrogen partial pressure is 5-6.5 MPa.
12. according to method described in claim 10 or 11, it is characterised in that the reaction temperature ratio of step (3) the catalysis reaction
The reaction temperature of step (1) the catalysis reaction is at least 50 DEG C high, and the hydrogen partial pressure of step (3) the catalysis reaction is than step (1)
At least high 2MPa of hydrogen partial pressure of the catalysis reaction.
13. according to the method for claim 1, it is characterised in that catalyst 2 described in step (5) 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%；The usage amount of catalyst 2 is reaction mass gross mass added by step (5) middle whole being added in catalytic reactor C
5%-20%.
14. according to the method for claim 13, it is characterised in that the usage amount of catalyst 2 is that catalysis is added in step (5)
The 10%-15% of reaction mass gross mass added by whole in reactor C.
15. according to the method for claim 13, it is characterised in that catalyst 2 described in step (5) 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 2.
16. according to the method for claim 1, it is characterised in that the reaction item of step (5) the Deep catalytic cracking reaction
Part are as follows: reaction temperature is 400-700 DEG C, and the 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.
17. according to the method for claim 16, it is characterised in that the reaction temperature of step (5) the Deep catalytic cracking reaction
Degree is 500-600 DEG C.
18. according to benefit require 16 or 17 described in method, it is characterised in that step (5) it is described catalysis reaction reaction temperature than step
Suddenly the reaction temperature of (3) described catalysis reaction is at least 50 DEG C high, and the hydrogen partial pressure of step (5) the catalysis reaction is than step (3) institute
State at least high 1MPa of hydrogen partial pressure of catalysis reaction.
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