CN108251146A - A kind of method of waste plastics and cellulose coprocessing - Google Patents
A kind of method of waste plastics and cellulose coprocessing Download PDFInfo
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- CN108251146A CN108251146A CN201810143303.7A CN201810143303A CN108251146A CN 108251146 A CN108251146 A CN 108251146A CN 201810143303 A CN201810143303 A CN 201810143303A CN 108251146 A CN108251146 A CN 108251146A
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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
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of methods of waste plastics and cellulose coprocessing.This method includes：Waste plastics is through the product obtained by catalytic pyrolysis, 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, 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 detached through gas-liquid-solid, the product liquid V of separation is respectively through tetrahydrofuran and thiacyclohexane extraction and separation, obtain product liquid VI and product liquid VII.This method not only increases overall conversion, and promotes the progress of goal response so as to improve liquid yield.
Description
Technical field
The invention belongs to fixed-end forces technical field, more particularly to a kind of waste plastics cooperates with processing to liquefy with cellulose
Method.
Background technology
The rubbish that the use of a large amount of plastic products generates not only has seriously polluted the environment, but also cause the waste of resource.
At present, plastic products consumption figure is huge, can all generate a large amount of waste plastic every year, but the recycling of waste plastics at present collect with
And classification effectiveness is generally relatively low, it is difficult to the various waste plastics of lasting supply, therefore individually treatment of waste plastics is hardly formed
Scale continuous production.Although the yield of cellulose is larger, it is at present much directly to incinerate, causes a large amount of air pollution
With the waste of resource.The liquefaction technology of plastics and the Optimum utilization of cellulose have had some researchs at present, if useless modeling
Material is added in cellulose copyrolysis processing together, can utilize the advantage of the two pyrolysis so that the production of the two valuable product
Amount is more increased.However, people to plastics and cellulose respectively direct liquefaction the study found that reaction condition and catalysis needed for the two
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 having certain challenge to waste plastics and cellulose.
Invention content
For shortcoming of the prior art, the present invention provides a kind of methods of waste plastics and cellulose coprocessing.
This method not only increases overall conversion ratio, and promote mesh compared with the treatment process of existing waste plastics and cellulose
The progress of reaction is marked, so as to improve liquid yield, improves the economic benefit and environmental benefit of entire technique.
A kind of method of waste plastics and cellulose coprocessing provided by the invention, includes the following steps：
(1) waste plastics is added in catalytic reactor A, catalytic cracking reaction, gained is carried out under the action of catalyst 1
Pyrolysis product be isolated to product liquid I, gas I and insoluble matter I；
(2) the product liquid I obtained by step (1) is passed through tetrahydrofuran successively 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 processing to remove solvent respectively, the product liquid II and product liquid III respectively obtained；
(4) the product liquid II obtained by cellulose and step (3) is 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 product liquid i obtained by step (4) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts
It takes, respectively obtains the tetrahydrofuran solution of the ii containing product liquid, the cyclohexane solution of the iii containing product liquid and the production of remaining liquid
Object iv by distilling processing to remove solvent, obtains product liquid ii and product liquid iii；
(6) remaining product liquid IV, remaining product liquid iv and the step respectively obtained to step (2) and step (5)
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, the pyrolysis product of gained is isolated to product liquid V, gas V and insoluble matter V；
(7) by the product liquid V obtained by step (6) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts
It takes, respectively obtains the tetrahydrofuran solution of the VI containing product liquid, the cyclohexane solution of the VII containing product liquid and the production of remaining liquid
Object VIII by distilling processing to remove solvent, obtains product liquid VI and product liquid VII.
In the present invention, described catalytic reactor A, B and C are slurry bed system catalytic cracking reaction device.
In the present invention, the waste plastics described in step (1) mainly includes polyethylene (PE), PP type plastics
(PP), the mixture of one or more of polystyrene (PS), total content is not less than the 80% of addition waste plastics gross mass.
In the present invention, the catalyst 1 described in step (1) is HY molecular sieve catalysts.The usage amount of the catalyst 1 is institute
Add the 5%-20% of waste plastics gross mass, preferably 10%-15%.
In the present invention, the reaction condition of the catalytic cracking reaction described in step (1) is as follows：Reaction temperature is 350-550 DEG C,
Preferably 400-480 DEG C；Reaction time is 30-150 minutes, preferably 45-120 minutes；Reaction carries out under stiring, stirring speed
Rate is 350-600 revs/min, preferably 400-500 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 2-4MPa is excellent
It is selected as 2.5-3.5MPa.
In the present invention, the cooling described in step (2), step (5) and step (7) is preferably cold by product liquid I, product liquid
I and product liquid V is but to room temperature.
In the present invention, distillation side of the distillation processing for this field routine described in step (3), step (5) and step (7)
Method, to remove tetrahydrofuran or thiacyclohexane solvent.
In the present invention, the cellulose described in step (4) is one kind in the plant fibers class substances such as stalk, bark, straw
It is or several.
In the present invention, the cellulose described in step (4) is added to before catalytic reactor B, preferably through pretreatment, such as powder
At least one of broken, dehydration.The wherein described crushing, the powder obtained by crushing, length are preferably more than
20mm.The dehydration carries out under anaerobic, and treatment temperature is 100-200 DEG C, processing time 60-120
Minute.
The product liquid II obtained by step (3), cellulose and product liquid II mass are added in the present invention, in step (4)
Than for 0.8-1.2:1.
In the present invention, the catalyst 2 described in step (4) is mixing one or two kinds of in iron naphthenate and molybdenum naphthenate
The mixture of object, preferably the two.The usage amount of the catalyst 2 is calculated as 800-1200ppm with the gross mass content of iron and molybdenum.
Mass content is added in while step (4) adds in catalyst 2, the sulphur source of 4000-8000ppm is calculated as vulcanizing agent using sulphur, be catalyzed
Sulfur content and the mass ratio of iron and molybdenum total content in reactor B are 5-7：1, wherein selected sulphur source for sulphur, hydrogen sulfide,
It is one or more in carbon disulfide etc..
In the present invention, the reaction condition of the 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 stir speed (S.S.) is
350-600 revs/min, preferably 400-500 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 4-8MPa, preferably
5-6.5MPa.Further, it is preferable to reaction condition it is as follows：The reaction temperature of step (4) the catalysis reaction is than step (1) institute
The reaction temperature for stating catalysis reaction is at least 50 DEG C high, and the hydrogen partial pressure catalysis more described than step (1) of step (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 catalysts, HZSM-5 with
The mass ratio 0.5-2 of HY：1, the HZSM-5 and HY composite molecular sieve catalysts, the quality of wherein phosphorus that preferably phosphorus and tungsten are modified contain
It is 1.5%~7.0% to measure, and the mass content of tungsten is 0.3%~2.0%.The usage amount of the catalyst 3 is to add in step (6)
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 3 is preferably as follows：HZSM-5 and HY carries 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 3 is obtained after molding.
In the present invention, conventional method molding, such as compression molding etc. may be used in the catalyst 3, in forming process
Shaping assistant can be added in as needed.It after compression molding, is sieved as needed, takes granular size as 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 are catalyzed with HY composite molecular screens
In agent phosphorus there may be form to be one or more in phosphotungstic acid, the oxide of phosphorus, phosphotungstate, phosphoric acid, phosphate etc.,
Tungsten is one or more in phosphotungstic acid, the oxide of tungsten, phosphotungstate etc. there may be form, it is preferred to use the above method
The catalyst of preparation.
In the present invention, the reaction condition of step (6) the Deep catalytic cracking reaction is：Reaction temperature is 400-700 DEG C,
Preferably 500-600 DEG C；Reaction time is 60-150 minutes；Reaction carries out under stiring, and stir speed (S.S.) is 350-600 revs/min
Clock；Need to be passed through hydrogen, hydrogen partial pressure 5-10MPa in reaction.Further, it is preferable to reaction condition it is as follows：Step (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 reaction catalysis reaction more described than step (4).
Compared with prior art, the present invention has the following advantages：
Cellulose and waste plastics are as two kinds of intractable solid waste rubbish, and the present invention is by the processing of cellulose with giving up
The catalytic pyrolysis of plastics is combined, while they are turned waste into wealth.The present invention makes full use of the characteristics of two kinds of reactions, reacts item
Part each self-optimizing again compared with conventional waste plastics and cellulose coprocessing, not only increases overall conversion ratio, and promote
The progress of goal response reduces insoluble object amount so as to improving the yield of hexamethylene soluble matter and tetrahydrofuran soluble matter.
It particularly will be jointly pyrolyzed by the product liquid that tetrahydrofuran is obtained by extraction and cellulose after waste plastics catalytic pyrolysis, help to carry
The dissolving of polarity improves the conversion ratio of cellulose in high-cellulose catalytic reaction process.In addition, the present invention by waste plastics and
Insoluble matter of the cellulose after catalysis is reacted collects mixing, and adds in after waste plastics and cellulose catalytic reaction not by tetrahydrofuran
With the remaining liq product of hexamethylene extraction, under the effect of the catalyst, Deep catalytic cracking reaction is carried out, reduces a large amount of waste residues
Generation.The HZSM-5 and HY composite molecular screens being modified for waste residue difficult to deal with, phosphorus and tungsten especially with the present invention
Catalyst, cracking temperature is more mild, and cleavage rate is high.
In addition, present invention process flow is simple, reaction condition is mild, simple and practicable, and cost is relatively low, solves a large amount of useless modelings
Material and cellulose processing are difficult, recycle the problem of value is low, not only slow down environment caused by a large amount of waste plastics and cellulose
Pressure, and turn waste into wealth, hence it is evident that improve the surcharge of waste plastics and cellulose.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention；
The reference numerals are as follows：1st, catalytic reactor A；2nd, gas-liquid-solid separator a；3rd, be equipped with successively with tetrahydrofuran and
Hexamethylene is the extraction equipment a of solvent；4th, catalytic reactor B；5th, gas-liquid solid separation device b；6th, it is equipped with successively with tetrahydrofuran
With the extraction equipment b that hexamethylene is solvent；7th, catalytic reactor C；8th, gas-solid separating device c；9th, it is equipped with successively with tetrahydrofuran
With the extraction equipment c that hexamethylene is solvent；21st, liquid product I；22nd, gas I；23 insoluble matter I；31st, product liquid II, 32, liquid
Body product III；33rd, remaining product liquid IV；51st, product liquid i；52nd, gas i；53rd, insoluble matter i；61st, product liquid ii；
62nd, product liquid iii；63rd, remaining product liquid iv；81st, product liquid V；82nd, gas V；83rd, insoluble matter V；91st, liquid produces
Object VI；92nd, product liquid VII；93rd, remaining product liquid VIII.
Specific embodiment
The method that waste plastics and fiber coprocessing are further illustrated the present invention with reference to specific embodiment, but this
The protection domain of invention and the range for being not so limited to following embodiment.Wt% representation quality scores wherein in the present embodiment.
As shown in Figure 1, the method for waste plastics provided by the invention and cellulose coprocessing, includes 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 product liquid I 21 obtained by step (1) be passed through successively after cooling equipped with using tetrahydrofuran and hexamethylene as
The extraction equipment a 3 of solvent is extracted, and respectively obtains the tetrahydrofuran solution of the II containing product liquid, the III containing product liquid
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 processing to remove solvent respectively, the product liquid II 31 and product liquid III 32 respectively obtained；
(4) cellulose is charged first in catalytic reactor B 4 and be carried out dehydrating, then added obtained by step (3)
Product liquid II 31, catalysis reaction is carried out under the action of catalyst 2, through 5 isolated liquid of gas-liquid-solid separator b produce
Object i 51, gas i 52 and insoluble matter i 53；
(5) the product liquid i 51 obtained by step (4) is passed through successively after cooling equipped with tetrahydrofuran and hexamethylene
Extraction equipment b 6 for solvent is extracted, and respectively obtains tetrahydrofuran solution, the iii containing product liquid of the ii containing product liquid
Cyclohexane solution and remaining product liquid iv 63, by distilling processing to remove solvent, obtain 61 Hes of product liquid ii
Product liquid iii 62；
(6) remaining product liquid IV 33, the remaining product liquid iv respectively obtained to step (2) and step (5)
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, the pyrolysis product of gained is isolated through gas-liquid solid separation device c 8
Product liquid V 81, gas V 82 and insoluble matter V 83；
(7) the product liquid V81 obtained by step (6) is passed through after cooling be equipped with successively using tetrahydrofuran and hexamethylene as
The extraction equipment c 9 of solvent is extracted, and respectively obtains the tetrahydrofuran solution of the VI containing product liquid, the VII containing product liquid
Cyclohexane solution and remaining product liquid VIII 93 by distilling processing to remove solvent, obtain 91 Hes of product liquid VI
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, in table 1 product for gas, hexamethylene soluble matter, tetrahydrofuran soluble matter, waste residue, 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 low-carbon alkene of the carbon such as ethylene and propylene below four.The present invention
The HZSM-5 and HY composite molecular sieve catalysts CAT-A that phosphorus and tungsten used in embodiment are modified is specific as follows：HZSM-5 is answered with HY
The mass ratio for closing molecular sieve is 1：1, the mass content of phosphorus is 3%, and the mass content of tungsten is 1.2%, and preparation method is as follows：
HZSM-5 is mixed with HY molecular sieves, is impregnated composite molecular screen with the phosphoric acid solution that mass concentration is 15%, is done at 100 DEG C
Dry 2 hours；Composite molecular screen is impregnated with the wolframic acid sodium water solution that mass concentration is 1.5%, it is 8 hours dry at 100 DEG C, finally
It is roasted 6 hours at 350 DEG C, through compression molding, sieving takes the solid particle that granular size is 40 mesh to 60 mesh as phosphorus and tungsten
Modified HZSM-5 and HY composite molecular sieve catalysts CAT-A.
HZSM-5 and HY composite molecular sieve catalysts CAT-B used in the embodiment of the present invention is specific as follows：HZSM-5 and HY
The mass ratio of composite molecular screen is 1：1, preparation method is as follows：HZSM-5 is mixed with HY composite molecular screens, at 100 DEG C
It is 8 hours dry, it is finally roasted 6 hours at 350 DEG C, through compression molding, sieving takes the solid that granular size is 40 mesh to 60 mesh
Particle is as HZSM-5 and HY composite molecular sieve catalysts CAT-B.
Embodiment 1
The common 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, be catalyzed under the catalytic action of HY molecular sieve catalysts
Cracking reaction, the additive amount of HY molecular sieves are the 12% of waste plastics gross mass, and the reaction condition of catalytic cracking reaction is as follows：Reaction
Temperature is 450 DEG C, and the reaction time is 60 minutes, and stir speed (S.S.) is 440 revs/min, needs to lead into catalytic reactor A in reaction
Enter hydrogen, hydrogen partial pressure 2.8MPa detaches the product after reaction, obtains product liquid I, gas I and insoluble matter I；It will
Product liquid I is cooled to after room temperature and is passed through tetrahydrofuran successively, cyclohexane solvent is extracted, and respectively obtains containing product liquid
The tetrahydrofuran solution of II, the cyclohexane solution of the III containing product liquid and remaining liquid product IV；To obtaining producing containing liquid
The tetrahydrofuran solution of object II and the cyclohexane solution of the III containing product liquid carry out distillation processing to remove solvent, obtained liquid
Body product II and product liquid III；2g stalks are crushed to the powder that length is about 10mm, are then taken off under anaerobic
Water process, treatment temperature are 130 DEG C, and processing time is 70 minutes, and the stalk after pre-processing is added to slurry bed system catalytic pyrolysis
In reactor B, the iron naphthenate and aphthenic acids of each 500ppm of mass content are then added in into slurry bed system catalytic cracking reaction device B
Molybdenum adds in sulphur that mass content is calculated as 6000ppm using sulphur as vulcanizing agent as catalyst, makes catalytic cracking reaction device
Sulfur content and the mass ratio of iron and molybdenum total content are 6 in B:1, and product liquid II is passed through slurry bed system catalytic cracking reaction device B,
Then it is reacted under following reaction condition：Reaction temperature is 520 DEG C, and the reaction time is 70 minutes, stir speed (S.S.) 430
Rev/min, the needs in reaction are passed through hydrogen, hydrogen partial pressure 5.6MPa, after reaction into slurry bed system catalytic cracking reaction device B
Product detached, obtain product liquid i, gas i and insoluble matter i；After the liquid product i of gained is cooled to room temperature successively
It is passed through tetrahydrofuran and cyclohexane solvent is extracted, obtain the tetrahydrofuran solution of the ii containing product liquid and containing product liquid
The cyclohexane solution of iii and remaining product liquid iv, and tetrahydrofuran solution to the ii containing product liquid and containing product liquid
The cyclohexane solution of iii 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 phosphorus and tungsten prepared by method described above is modified is compound
For molecular sieve as catalyst CAT-A, the usage amount of the catalyst is all reactions added in slurry bed system catalytic cracking reaction device C
The 12% of material gross mass carries out Deep catalytic cracking reaction under following reaction condition：Reaction temperature is 570 DEG C, during reaction
Between for 100 minutes, 440 revs/min of stir speed (S.S.), the needs in reaction are passed through hydrogen into slurry bed system catalytic cracking reaction device C,
Its hydrogen partial pressure is 7.0MPa, and the pyrolysis product of gained is isolated to product liquid V, gas V and insoluble matter V；By the liquid of gained
Body product V is passed through tetrahydrofuran successively after cooling, cyclohexane solvent is extracted, and respectively obtains the tetrahydrochysene of the VI containing product liquid
Tetrahydrofuran solution, the cyclohexane solution of the VII containing product liquid and remaining product liquid VIII, it is molten to remove by distilling processing
Agent obtains product liquid VI and product liquid VII.
Embodiment 2
Only the reaction condition of catalytic cracking reaction carried out in slurry bed system catalytic cracking reaction device A will be urged in embodiment 1
It is changed to：Reaction temperature is 470 DEG C, and the reaction time is 95 minutes, and stir speed (S.S.) 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 3.2MPa, slurry bed system catalytic cracking reaction device C carry out Deep catalytic and split
The condition of solution reaction is changed to：Reaction temperature is 590 DEG C, and the reaction time is 80 minutes, 500 revs/min of stir speed (S.S.), in reaction
It needs to be passed through hydrogen, hydrogen partial pressure 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 the reaction condition of catalytic cracking reaction device B is changed to：Reaction temperature is 510 DEG C, and hydrogen partial pressure is
6.0MPa, 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.
Comparative example 1
It takes the common 2g of mixture of three kinds of plastics of 50wt%HDPE, 30wt%PET, 20wt%PS, be crushed to 2g stalks
It is added in slurry bed system catalytic cracking reaction device, in the catalysis of HY molecular sieve catalysts by the powder of length about 10mm jointly
Effect is lower to carry out catalytic cracking reaction, and the additive amount of HY molecular sieves is the 12% of waste plastics and cellulose gross mass, catalytic pyrolysis
The reaction condition of reaction is as follows：Reaction temperature is 520 DEG C, and the reaction time is 70 minutes, and stir speed (S.S.) is 430 revs/min, reaction
In need to be passed through hydrogen into slurry bed system catalytic cracking reaction device, hydrogen partial pressure 5.6MPa detaches the product after reaction,
Obtain product liquid 1, gas and waste residue；Product liquid 1 is cooled to after room temperature and is passed through tetrahydrofuran, cyclohexane solvent successively
It is extracted, respectively obtains the tetrahydrofuran solution containing product liquid 2, the cyclohexane solution containing product liquid 3 and remaining liquid
State product IV, and the tetrahydrofuran solution containing product liquid 2, the cyclohexane solution containing product liquid 3 are distilled to remove
Solvent obtains product liquid 2 and product liquid 3.
The distribution of 1 embodiment 1-5 of table and 1 products therefrom of comparative example and conversion ratio comparison
| Number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Product is distributed, % | ||||||
| Gas | 3.8 | 9.7 | 9.5 | 8.0 | 8.9 | 13.5 |
| Hexamethylene soluble matter | 29.2 | 40.4 | 32.8 | 34.5 | 28.6 | 19.8 |
| Tetrahydrofuran soluble matter | 54.2 | 45.8 | 44.3 | 43.2 | 38.5 | 24.2 |
| Residue | 12.8 | 4.1 | 13.4 | 14.3 | 24.0 | 42.5 |
| Conversion ratio, % | 87.2 | 95.9 | 86.6 | 85.7 | 76.0 | 57.5 |
Claims (10)
1. a kind of method of waste plastics and cellulose coprocessing, includes the following steps：
(1) waste plastics is added in catalytic reactor A, catalytic cracking reaction is carried out under the action of catalyst 1, gained is split
Solution product is isolated to product liquid I, gas I and insoluble matter I；
(2) the product liquid I obtained by step (1) is passed through tetrahydrofuran successively 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 of the II containing product liquid obtained to step (2) and the III containing product liquid point
Distillation processing is not carried out to remove solvent, the product liquid II and product liquid III respectively obtained；
(4) cellulose and the product liquid II obtained by step (3) 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 product liquid i obtained by step (4) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts, point
The tetrahydrofuran solution of the ii containing product liquid, the cyclohexane solution of the iii containing product liquid and remaining product liquid iv are not obtained,
By distilling processing to remove solvent, product liquid ii and product liquid iii are obtained；
(6) remaining product liquid IV, remaining product liquid iv and the step (1) respectively obtained to step (2) and step (5)
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, the pyrolysis product of gained are isolated to product liquid V, gas V and insoluble matter V；
(7) by the product liquid V obtained by step (6) is passed through tetrahydrofuran successively after cooling, cyclohexane solvent extracts, point
The tetrahydrofuran solution of the VI containing product liquid, the cyclohexane solution of the VII containing product liquid and remaining product liquid are not obtained
VIII by distilling processing to remove solvent, obtains product liquid VI and product liquid VII.
2. 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%.
3. according to the method for claim 1, it is characterised in that the catalyst 1 described in step (1) is HY molecular sieve catalysts,
The usage amount of catalyst 1 is the 5%-20%, preferably 10%-15% of added waste plastics gross mass.
4. according to the method for claim 1, it is characterised in that the reaction condition of the catalytic cracking reaction described in step (1) is such as
Under：Reaction temperature is 350-550 DEG C, preferably 400-480 DEG C；Reaction time is 30-150 minutes, preferably 45-120 minutes；
Reaction carries out under stiring, and stir speed (S.S.) is 350-600 revs/min, preferably 400-500 revs/min；It needs to be passed through in reaction
Hydrogen, preferably hydrogen partial pressure 2-4MPa, 2.5-3.5MPa.
5. according to the method for claim 1, it is characterised in that the cellulose described in step (4) is stalk, bark, straw are planted
One or more of fibres class substance；The cellulose is added to before catalytic reactor B, is first pre-processed, described
Pretreatment includes at least one of pulverization process, dehydration, of length no more than 20mm of cellulose substances after pulverization process,
The dehydration carries out under anaerobic, and treatment temperature is 100-200 DEG C, and processing time is 60-120 minutes.
6. according to the method for claim 1, it is characterised in that the catalyst 2 described in step (4) is iron naphthenate and cycloalkanes
The mixture of one or two kinds of mixture in sour molybdenum, preferably the two；The usage amount of catalyst 2 is with the gross mass of iron and molybdenum
Content is calculated as 800-1200ppm；Mass content is added in while step (4) adds in catalyst 2,4000-8000ppm is calculated as with sulphur
Sulphur source as vulcanizing agent, sulfur content and the mass ratio of iron and molybdenum total content in catalytic reactor B are 5-7：1, it is selected
Sulphur source has：It is one or more in sulphur, hydrogen sulfide, carbon disulfide.
7. according to the method for claim 1, it is characterised in that the reaction condition of the catalysis reaction described in step (4) is as follows：
Reaction temperature is 400-600 DEG C, preferably 450-550 DEG C；Reaction time is 30-100 minutes, preferably 60-100 minutes；Instead
It should carry out under stiring, stir speed (S.S.) is 350-600 revs/min, preferably 400-500 revs/min；It needs to be passed through hydrogen in reaction
Gas, preferably hydrogen partial pressure 4-8MPa, 5-6.5MPa；Further, it is preferable to reaction condition it is as follows：Step (4) described catalysis
The reaction temperature of the reaction temperature of reaction catalysis reaction more described than step (1) is at least 50 DEG C high, step (4) the catalysis reaction
At least high 2MPa of hydrogen partial pressure of hydrogen partial pressure catalysis reaction more described than step (1).
8. according to the method for claim 1, it is characterised in that the catalyst 3 described in step (6) is compound for HZSM-5 and HY
The HZSM-5 that molecular sieve catalyst, preferably phosphorus and tungsten are modified and HY composite molecular sieve catalysts, the mass content of wherein phosphorus are
1.5%~7.0%, the mass content of tungsten is 0.3%~2.0%；The usage amount of catalyst 3 is anti-to add in catalysis in step (6)
Answer the 5%-20% of reaction mass gross mass added by the whole in device C, preferably 10%-15%.
9. according to the method described in claim 1 or 8, it is characterised in that the preparation method of the catalyst 3 described in step (6) is：
HZSM-5 and HY is with mass ratio 0.5-2:1 carries out being mixed to get composite molecular screen, with the phosphoric acid that mass concentration is 10%~20%
The mass ratio of solution dipping composite molecular screen, phosphoric acid solution and composite molecular screen is 0.5-1:1, the dry 1-3 at 80-110 DEG C
Hour, then impregnate composite molecular screen, sodium tungstate solution and composite molecular screen with the sodium tungstate solution that mass concentration is 1%~2%
Mass ratio be 0.5-1:1, it is 5-10 hours dry at 80-110 DEG C, it then roasts 4-7 hours, is molded at 330-380 DEG C
After obtain catalyst 3.
10. according to the method for claim 1, it is characterised in that the reaction item of step (6) the Deep catalytic cracking reaction
Part is：Reaction temperature is 400-700 DEG C, preferably 500-600 DEG C；Reaction time is 60-150 minutes；Reaction under stiring into
Row, stir speed (S.S.) are 350-600 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 5-10MPa, further, it is preferable to
Reaction condition it is as follows：The reaction temperature of the reaction temperature catalysis reaction more described than step (4) of step (6) the catalysis reaction is extremely
It is few 50 DEG C high, at least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure catalysis reaction more described than step (4) of step (6) the catalysis reaction.
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| WO2010025525A1 (en) * | 2008-09-05 | 2010-03-11 | Sheima Pty Ltd. | A process for producing synthetic fuels from waste and other materials |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
| CN101896582A (en) * | 2007-12-12 | 2010-11-24 | 雪佛龙美国公司 | System and method for producing transportation fuels from waste plastic and biomass |
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2018
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Patent Citations (4)
| 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 |
| CN101896582A (en) * | 2007-12-12 | 2010-11-24 | 雪佛龙美国公司 | System and method for producing transportation fuels from waste plastic and biomass |
| WO2010025525A1 (en) * | 2008-09-05 | 2010-03-11 | Sheima Pty Ltd. | A process for producing synthetic fuels from waste and other materials |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
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