CN108273558B - Catalytic cracking catalyst and its preparation method and application - Google Patents
Catalytic cracking catalyst and its preparation method and application Download PDFInfo
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- CN108273558B CN108273558B CN201810143298.XA CN201810143298A CN108273558B CN 108273558 B CN108273558 B CN 108273558B CN 201810143298 A CN201810143298 A CN 201810143298A CN 108273558 B CN108273558 B CN 108273558B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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Abstract
The invention discloses a kind of catalytic cracking catalysts and its preparation method and application.The catalyst is using kaolin and montmorillonite as carrier, using molybdenum naphthenate and/or iron naphthenate as active component, preparation method includes: that kaolin and montmorillonite original powder are added in reactor after high-temperature roasting, then iron naphthenate is added and/or the diluted acid maceration extract of molybdenum naphthenate is impregnated, catalytic cracking catalyst is made through drying in material after reaction.The catalytic cracking catalyst can be applied in the technique of processing cellulose and waste plastics, not only increase the overall conversion of cellulose and waste plastics, and promote 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 catalytic cracking catalyst and preparation method thereof and answer
With.
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 catalytic cracking catalyst and preparation method thereof and
Using.The conversion ratio of catalytic cracking reaction can be improved in the catalytic cracking catalyst, and promotes the progress of goal response, from
And liquid yield is improved, it is applied in waste plastics and fiber treatment technique, the economic benefit and environment of entire technique can be improved
Benefit.
First aspect present invention provides a kind of catalytic cracking catalyst, and the catalytic cracking catalyst is with kaolin and Meng Tuo
Soil is carrier, using molybdenum naphthenate and/or iron naphthenate as active component, with the poidometer of catalytic cracking catalyst, kaolin and
Montmorillonite accounts for 37.5%-87.5% altogether, and the mass ratio of kaolin and montmorillonite is 2.5-1:1, molybdenum naphthenate and/or iron naphthenate
Account for 12.5%-62.5%, preferably kaolin and montmorillonite accounts for 50%-70%, and the mass ratio of kaolin and montmorillonite is 2-1:
1, molybdenum naphthenate and/or iron naphthenate account for 30%-50%.
Second aspect of the present invention provides a kind of preparation method of above-mentioned catalytic cracking catalyst, and this method includes following step
It is rapid:
1) by kaolin and Meng Tuo in 400-550 DEG C of roasting 2-10h, 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, are then added into reaction vessel
The diluted acid maceration extract of iron naphthenate and/or molybdenum naphthenate is impregnated, and dipping while is preferably stirred, stirring rate 100-
150r/min, mixing time 0.5-2.5h；
3) material after step 2) reaction is dried under the conditions of 100-150 DEG C 2-6h, catalytic cracking catalyst is made.
The preparation method of the catalytic cracking catalyst, diluted acid described in step 2) are in hydrochloric acid, nitric acid and acetic acid
At least one, the mass concentration of diluted acid maceration extract is 5%-20%.
The maceration extract can use organic solution, preferred alcohol solution.The dipping uses conventional impregnation method, than
Such as it is saturated infusion process or supersaturated infusion process.
Catalytic cracking catalyst of the invention can be formed using conventional method, such as compression molding etc., in forming process
It can according to need addition shaping assistant.In the present invention, resulting material after step (3) drying can be formed, thus
Obtain molding catalytic cracking catalyst.It after compression molding, is sieved as needed, takes granular size for 30 mesh to 70
Mesh, preferably 40 to 60 mesh.
Third aspect present invention provides a kind of application of above-mentioned catalytic cracking catalyst, which can be with
Applied in the technique of processing cellulose and waste plastics, comprising the following steps:
(1) waste plastics is added in catalytic reactor A, carries out catalytic cracking reaction, gained under the action of catalyst 1
Pyrolysis product be isolated to product liquid I, gas I and insoluble matter I；
(2) the resulting product liquid I of step (1) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted,
Respectively obtain the tetrahydrofuran solution of the II containing product liquid, the cyclohexane solution of the III containing product liquid and remaining product liquid
IV；
(3) tetrahydrofuran solution of the II containing product liquid obtained to step (2) and the hexamethylene of the III containing product liquid are molten
Liquid carries out distillation respectively and handles to remove solvent, the product liquid II and product liquid III that respectively obtain；
(4) cellulose and step (3) resulting product liquid II are added in catalytic reactor B, in the effect of catalyst 2
Under carry out catalysis reaction, be isolated to product liquid i, gas i and insoluble matter i；
(5) by the resulting product liquid i of step (4) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent extracts
It takes, respectively obtains the tetrahydrofuran solution of the ii containing product liquid, the cyclohexane solution of the iii containing product liquid and remaining liquid and produce
Object iv obtains product liquid ii and product liquid iii by distillation processing to remove solvent；
(6) remaining product liquid IV, remaining product liquid iv and the step that step (2) and step (5) are respectively obtained
Suddenly the insoluble matter I and insoluble matter i that (1) and step (4) respectively obtain are added in catalytic reactor C, under the action of catalyst 3
Deep catalytic cracking reaction is carried out, resulting pyrolysis product is isolated to product liquid V, gas V and insoluble matter V；
(7) by the resulting product liquid V of step (6) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent extracts
It takes, respectively obtains the tetrahydrofuran solution of the VI containing product liquid, the cyclohexane solution of the VII containing product liquid and remaining liquid and produce
Object VIII obtains product liquid VI and product liquid VII by distillation processing to remove solvent；
Wherein, catalyst 2 is using catalytic cracking catalyst described in above-mentioned first aspect and second aspect.
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, catalyst 1 described in step (1) is HY molecular sieve catalyst.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 catalytic cracking reaction described in step (1) is as follows: reaction temperature is 350-550 DEG C,
Preferably 400-480 DEG C；Reaction time is 30-150 minutes, preferably 45-120 minutes；Reaction carries out under stiring, stirring speed
Rate is 350-600 revs/min, preferably 400-500 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 2-4MPa is excellent
It is selected as 2.5-3.5MPa.
In the present invention, cooling described in step (2), step (5) and step (7) is preferably 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 (3), step (5) and step (7) is the distillation side of this field routine
Method, to remove tetrahydrofuran or thiacyclohexane solvent.
In the present invention, cellulose described in step (4) is one of plant fibers substances such as stalk, bark, straw
Or it is several.
In the present invention, cellulose described in step (4) is added to before catalytic reactor B, preferably through pretreatment, such as powder
At least one of broken, dehydration.Wherein the crushing, the powder obtained by crushing, length are preferably more than
20mm.The dehydration carries out under anaerobic, and treatment temperature is 100-200 DEG C, and the processing time is 60-120
Minute.
In the present invention, step (3) resulting product liquid II, cellulose and product liquid II mass are added in step (4)
Than for 0.8-1.2:1.
In the present invention, the usage amount of catalyst 2 described in step (4) accounts for the 2.5%-15% of added cellulose quality.Step
Suddenly mass content is added while catalyst 2 are added in (4), the sulphur source of 4000-8000ppm is calculated as vulcanizing agent, sulfur content using sulphur
It is 5-7:1 with the mass ratio of iron and molybdenum total content, wherein selected sulphur source is one in sulphur, hydrogen sulfide, carbon disulfide etc.
Kind is a variety of.
In the present invention, the reaction condition of catalysis reaction described in step (4) is as follows: reaction temperature is 400-600 DEG C, preferably
It is 450-550 DEG C；Reaction time is 30-100 minutes, preferably 60-100 minutes；Reaction carries out under stiring, and stirring rate is
350-600 revs/min, preferably 400-500 revs/min；Need to be passed through hydrogen in reaction, hydrogen partial pressure 4-8MPa, preferably
5-6.5MPa.Further, it is preferable to reaction condition it is as follows: step (4) it is described catalysis reaction reaction temperature than step (1) institute
The reaction temperature for stating catalysis reaction is at least 50 DEG C high, and the hydrogen partial pressure catalysis more described than step (1) of step (4) the catalysis reaction is anti-
At least high 2MPa of the hydrogen partial pressure answered.
In the present invention, catalyst 3 described in step (6) is HZSM-5 and HY composite molecular sieve catalyst, HZSM-5 with
The mass ratio 0.5-2:1 of HY, preferably phosphorus and tungsten modified HZSM-5 and HY composite molecular sieve catalyst, wherein the quality of phosphorus contains
Amount is 1.5%-7.0%, and the mass content of tungsten is 0.3%-2.0%.The usage amount of the catalyst 3 is to be added in step (6)
The 5%-18% of reaction mass gross mass, preferably 8%-13% added by whole in catalytic reactor C.
In the present invention, the preparation method of used catalyst 3 is preferably as follows: HZSM-5 and HY carry out being mixed to get compound molecule
Sieve impregnates composite molecular screen with the phosphoric acid solution that mass concentration is 10%-20%, 1-3 hours dry at 80-110 DEG C；Use matter
The wolframic acid sodium water solution that amount concentration is 1%-2% impregnates composite molecular screen again, 5-10 hours dry at 80-110 DEG C, finally
It is roasted 4-7 hours at 330-380 DEG C, catalyst 3 is obtained after molding.
In the present invention, the catalyst 3 can be formed using conventional method, such as compression molding etc., in forming process
It can according to need addition shaping assistant.It after compression molding, is sieved as needed, takes granular size for 30 mesh to 70
Mesh, preferably the solid particle of 40 to 60 mesh is as catalyst 3.The phosphorus and tungsten modified HZSM-5 and HY composite molecular screen is catalyzed
In agent phosphorus there may be form be one of phosphotungstic acid, the oxide of phosphorus, phosphotungstate, phosphoric acid, phosphate etc. or it is a variety of,
Tungsten there may be form be one of phosphotungstic acid, the oxide of tungsten, phosphotungstate etc. or it is a variety of, it is preferred to use the above method
The catalyst of preparation.
In the present invention, the reaction condition of step (6) the Deep catalytic cracking reaction are as follows: reaction temperature is 400-700 DEG C,
Preferably 500-600 DEG C；Reaction time is 60-150 minutes；Reaction carries out under stiring, and stirring rate is 350-600 revs/min
Clock；Need to be passed through hydrogen, hydrogen partial pressure 5-10MPa in reaction.Further, it is preferable to reaction condition it is as follows: step (6) institute
The reaction temperature for stating the reaction temperature catalysis reaction more described than step (4) of catalysis reaction is at least 50 DEG C high, step (6) described catalysis
At least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure of the reaction catalysis reaction more described than step (4).
Compared with prior art, the invention has the following advantages that
The present invention provides catalytic cracking catalyst, using kaolin and montmorillonite as carrier, with molybdenum naphthenate and/or ring
Alkanoic acid iron is active component, which is more advantageous to the catalytic pyrolysis of cellulose, and it is suitable for waste plastics and fibre
In the technique for tieing up plain coprocessing, is conducive to the generation of target product, while being also beneficial to catalyst and separating from raw material, subtracts
Further pollution of the small catalyst to raw material.
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 the product liquid being obtained by extraction after waste plastics catalytic pyrolysis by tetrahydrofuran is pyrolyzed jointly with cellulose, and in this hair
Under the action of the catalytic cracking catalyst of bright offer, it is more conducive to improve the dissolution of polarity in cellulose catalytic reaction process
Improve the conversion ratio of cellulose.In addition, the insoluble matter of waste plastics and cellulose after catalysis reaction is collected mixing by the present invention, and
The remaining liq product not extracted by tetrahydrofuran and hexamethylene after waste plastics and cellulose catalytic reaction is added, in catalyst
Under effect, Deep catalytic cracking reaction is carried out, the generation of a large amount of waste residues is reduced.For waste residue difficult to deal with, especially with
The HZSM-5 and HY composite molecular sieve catalyst that phosphorus of the invention and tungsten are modified, cracking temperature is more mild, and cleavage rate is high.
In addition, present invention process process is simple, reaction condition is mild, simple and easy, and cost is relatively low, solves a large amount of useless modelings
Material and cellulose processing hardly possible, recycling are worth low problem, not only slow down environment caused by a large amount of waste plastics and cellulose
Pressure, and turn waste into wealth, hence it is evident that improve the surcharge of waste plastics and cellulose.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention；
The reference numerals are as follows: 1, catalytic reactor A；2, gas-liquid-solid separator a；3, be successively arranged with tetrahydrofuran and
Hexamethylene is the extraction equipment a of solvent；4, catalytic reactor B；5, gas-liquid solid separation device b；6, it is successively arranged with tetrahydrofuran
It is the extraction equipment b of solvent with hexamethylene；7, catalytic reactor C；8, gas-solid separating device c；9, it is successively arranged with tetrahydrofuran
It is the extraction equipment c of solvent with hexamethylene；21, liquid product I；22, gas I；23 insoluble matter I；31, product liquid II, 32, liquid
Body product III；33, remaining product liquid IV；51, product liquid i；52, gas i；53, insoluble matter i；61, product liquid ii；
62, product liquid iii；63, remaining product liquid iv；81, product liquid V；82, gas V；83, insoluble matter V；91, liquid produces
Object VI；92, product liquid VII；93, remaining product liquid VIII.
Specific embodiment
The application of catalytic cracking catalyst of the present invention is further illustrated below with reference to specific embodiment, but it is of the invention
Protection scope and be not so limited to the range of following embodiment.In the present invention, wt% representation quality score.
As shown in Figure 1, the application of catalytic cracking catalyst provided by the invention, 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), which is successively passed through to be equipped with tetrahydrofuran and hexamethylene after cooling, is
The extraction equipment a 3 of solvent is extracted, and the tetrahydrofuran solution of the II containing product liquid, the III containing product liquid are respectively obtained
Cyclohexane solution and remaining product liquid IV 33；
(3) tetrahydrofuran solution of the II containing product liquid obtained to step (2) and the hexamethylene of the III containing product liquid are molten
Liquid carries out distillation respectively and handles to remove solvent, the product liquid II 31 and product liquid III 32 that respectively obtain；
(4) cellulose is charged first in catalytic reactor B 4 and is carried out dehydrating, then added obtained by step (3)
Product liquid II 31, carry out catalysis reaction under the action of catalyst 2, through the isolated liquid of gas-liquid-solid separator b 5 produce
Object i 51, gas i 52 and insoluble matter i 53；
(5) the resulting product liquid i 51 of step (4) is successively passed through after cooling and is equipped with tetrahydrofuran and hexamethylene
It is extracted for the extraction equipment b 6 of solvent, respectively obtains tetrahydrofuran solution, the iii containing product liquid of the ii containing product liquid
Cyclohexane solution and remaining product liquid iv 63, by distillation processing to remove solvent, obtain 61 He of product liquid ii
Product liquid iii 62；
(6) remaining product liquid IV 33, the remaining product liquid iv that step (2) and step (5) are respectively obtained
63 and step (1) and step (4) the insoluble matter I 23 that respectively obtains and insoluble matter I 53 be added in catalytic reactor C 7,
Deep catalytic cracking reaction is carried out under the action of catalyst 3, resulting pyrolysis product is isolated through gas-liquid solid separation device c 8
Product liquid V 81, gas V 82 and insoluble matter V 83；
(7) the resulting product liquid V81 of step (6) is passed through to be successively arranged after cooling and is with tetrahydrofuran and hexamethylene
The extraction equipment c 9 of solvent is extracted, and the tetrahydrofuran solution of the VI containing product liquid, the VII containing product liquid are respectively obtained
Cyclohexane solution and remaining product liquid VIII 93 obtain 91 He of product liquid VI by distillation processing to remove solvent
Product liquid VII 92.
Wherein, insoluble matter V 83 is the waste residue for not continuing to participate in reaction, and remaining product liquid VIII 93 can be recycled
Further catalytic cracking reaction is carried out to catalytic reactor C 7.
Wherein, product is gas, hexamethylene soluble matter, tetrahydrofuran soluble matter, waste residue in table 1, wherein gas is gas
I 22, gas i 52 and gas V82, thiacyclohexane soluble matter are product liquid III 32, product liquid iii 62 and product liquid
VII 92, tetrahydrofuran soluble matter are product liquid ii 61 and product liquid VI 91, and residue is insoluble matter V 83 and residue
Product liquid VIII 93.Conversion ratio refers to that gas in product, hexamethylene soluble matter, tetrahydrofuran soluble matter gross mass account for
The percentage of four kinds of product qualities.In the present invention, gas is mainly the low-carbon alkene below of the carbon such as ethylene and propylene four.
The preparation method of used catalyst of embodiment of the present invention 2-A is specific as follows: 1) kaolin and montmorillonite original powder existing
430 DEG C of roasting 6h, wherein the heating rate for being warming up to maturing temperature is 7 DEG C/min；2) kaolinite that will be obtained after step 1) roasting
Soil is added in reactor, and the maceration extract that the dilute hydrochloric acid of iron naphthenate and molybdenum naphthenate is then added into reactor carries out supersaturation
Dipping, maceration extract dosage are 1.2 times of saturation absorption water theory dosage, and maceration extract is ethanol solution, wherein the quality of hydrochloric acid point
Number is 12%, is stirred, stirring rate 125r/min, mixing time 1.5h；3) by the material after step 2) reaction at 130 DEG C
Under the conditions of dry 4h, then through compression molding, sieving takes solid particle that granular size is 40 mesh to 60 mesh as catalyst 2-A,
The material of addition meets: with the poidometer of the catalytic cracking catalyst, the mass ratio of kaolin and montmorillonite is 2:1, kaolin
60% is accounted for altogether with montmorillonite, and iron naphthenate accounts for 20%, molybdenum naphthenate and accounts for 20%.
The preparation method of catalyst 2-B used in the embodiment of the present invention is specific as follows: will be in the preparation method of catalyst 2-A
The dilute hydrochloric acid material that is changed to acetic acid, and is added meet: with the poidometer of the catalytic cracking catalyst, kaolin and montmorillonite
Mass ratio is 2:1, and kaolin and montmorillonite account for 62% altogether, and iron naphthenate accounts for 18%, molybdenum naphthenate and accounts for 20%, other same catalyst
The preparation method of 2-A.
The preparation method of catalyst 2-C used in the embodiment of the present invention is specific as follows: the material of addition meets: with the catalysis
The mass ratio of the poidometer of catalyst for cracking, kaolin and montmorillonite is 1.5:1, and kaolin and montmorillonite montmorillonite account for 55%,
Iron naphthenate accounts for 23%, molybdenum naphthenate and accounts for 22%, the preparation method of other same catalyst 2-A.
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, be catalyzed under the catalytic action of HY molecular sieve catalyst
Cracking reaction, the additive amount of HY molecular sieve are the 12% of waste plastics gross mass, and the reaction condition of catalytic cracking reaction is as follows: reaction
Temperature is 440 DEG C, and the reaction time is 60 minutes, and stirring rate is 440 revs/min, needs to lead into catalytic reactor A in reaction
Enter hydrogen, hydrogen partial pressure 2.7MPa separates 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 successively passed through tetrahydrofuran, 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；It is produced to what is obtained 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 stalk is crushed to the powder that length is about 10mm, is then taken off under anaerobic
Water process, treatment temperature are 130 DEG C, and the processing time is 70 minutes, and the stalk after pre-processing is added to slurry bed system catalytic pyrolysis
In reactor B, catalyst 2-A is then added into slurry bed system catalytic cracking reaction device B, the usage amount of catalyst 2-A accounts for added
The 7% of cellulose, while sulphur that mass content is calculated as 6000ppm using sulphur is added as vulcanizing agent, make catalytic cracking reaction device B
The mass ratio of middle sulfur content and iron and molybdenum total content is 6:1, and product liquid II is passed through slurry bed system catalytic cracking reaction device B,
Then reacted under following reaction condition: reaction temperature is 510 DEG C, and the reaction time is 70 minutes, stirring rate 430
Rev/min, the needs in reaction are passed through hydrogen, hydrogen partial pressure 5.4MPa, after reaction into slurry bed system catalytic cracking reaction device B
Product separated, obtain product liquid i, gas i and insoluble matter i；After resulting liquid product i 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 contain 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 the phosphorus in the above way prepared and tungsten are modified is compound
For molecular sieve as catalyst CAT-A, the usage amount of the catalyst is all reactions being added in slurry bed system catalytic cracking reaction device C
The 10% of material gross mass, Deep catalytic cracking reaction is carried out under following reaction condition: reaction temperature is 570 DEG C, when reaction
Between be 100 minutes, 440 revs/min of stirring rate, the needs in reaction are passed through hydrogen into slurry bed system catalytic cracking reaction device C,
Its hydrogen partial pressure is 7.0MPa, and resulting pyrolysis product is isolated to product liquid V, gas V and insoluble matter V；By resulting liquid
Body product V is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted, and respectively obtains the tetrahydro of the VI containing product liquid
The cyclohexane solution and remaining product liquid VIII of tetrahydrofuran solution, the VII containing product liquid, it is molten to remove by distillation processing
Agent obtains product liquid VI and product liquid VII.
Embodiment 2
The reaction condition of the catalytic cracking reaction carried out in slurry bed system catalytic cracking reaction device A will be only urged in embodiment 1
Be changed to: reaction temperature is 460 DEG C, and the reaction time is 120 minutes, and stirring rate is 480 revs/min, is needed in reaction to slurry
Hydrogen is passed through in bed catalytic cracking reaction device A, hydrogen partial pressure 3.2MPa, slurry bed system catalytic cracking reaction device C carry out Deep catalytic
The condition of cracking reaction is changed to: reaction temperature be 590 DEG C, the reaction time be 80 minutes, 500 revs/min of stirring rate, in reaction
Needs be passed through hydrogen, hydrogen partial pressure 7.0MPa into slurry bed system catalytic cracking reaction device C.
Embodiment 3
Only change the catalyst 2-A in embodiment 1 into catalyst 2-B, the usage amount of catalyst 2-B accounts for added cellulose
5%, the other the same as in Example 1.
Embodiment 4
Only change the catalyst 2-A in embodiment 1 into catalyst 2-C, the usage amount of catalyst 2-C accounts for added cellulose
8%, the other the same as in Example 1.
Embodiment 5
Change the catalyst CAT-A in embodiment 1 into CAT-B, the other the same as in Example 1.
Comparative example 1
It takes the total 2g of mixture of three kinds of plastics of 50wt%HDPE, 30wt%PET, 20wt%PS, be crushed to 2g 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 1-5 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 distribution, wt% | ||||||
| Gas | 8.7 | 8.4 | 9.2 | 9.3 | 8.8 | 13.5 |
| Hexamethylene soluble matter | 31.5 | 33.6 | 32.1 | 35.2.5 | 28.9 | 19.8 |
| Tetrahydrofuran soluble matter | 50.6 | 46.7 | 50.7 | 44.7 | 40.4 | 24.2 |
| Residue | 9.2 | 11.3 | 8.0 | 10.8 | 21.9 | 42.5 |
| Conversion ratio, wt% | 90.8 | 88.7 | 92.0 | 89.2 | 78.1 | 57.5 |
Claims (20)
1. a kind of application of catalytic cracking catalyst in processing cellulose and waste plastics technique, comprising the following steps:
(1) waste plastics is added in catalytic reactor A, catalytic cracking reaction is carried out under the action of catalyst 1, it is resulting to split
Solution product is isolated to product liquid I, gas I and insoluble matter I；
(2) the resulting product liquid I of step (1) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent is extracted, respectively
Obtain the tetrahydrofuran solution of the II containing product liquid, the cyclohexane solution of the III containing product liquid and remaining product liquid IV；
(3) cyclohexane solution of the tetrahydrofuran solution for the II containing product liquid that step (2) is obtained and the III containing product liquid point
It does not carry out distillation to handle to remove solvent, the product liquid II and product liquid III that respectively obtain；
(4) cellulose and step (3) resulting product liquid II are added in catalytic reactor B, under the action of catalyst 2 into
Row catalysis reaction, is isolated to product liquid i, gas i and insoluble matter i；
(5) by the resulting product liquid i of step (4) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent extracts, point
The tetrahydrofuran solution of the ii containing product liquid, the cyclohexane solution of the iii containing product liquid and remaining product liquid iv are not obtained,
By distillation processing to remove solvent, product liquid ii and product liquid iii are obtained；
(6) remaining product liquid IV, remaining product liquid iv and the step (1) that step (2) and step (5) are respectively obtained
The insoluble matter I and insoluble matter i respectively obtained with step (4) is added in catalytic reactor C, is carried out under the action of catalyst 3
Deep catalytic cracking reaction, resulting pyrolysis product are isolated to product liquid V, gas V and insoluble matter V；
(7) by the resulting product liquid V of step (6) is successively passed through tetrahydrofuran after cooling, cyclohexane solvent extracts, point
The tetrahydrofuran solution of the VI containing product liquid, the cyclohexane solution of the VII containing product liquid and remaining product liquid are not obtained
VIII obtains product liquid VI and product liquid VII by distillation processing to remove solvent；
Wherein the catalyst 1 is HY molecular sieve catalyst, and the catalyst 3 is HZSM-5 and HY composite molecular screen is catalyzed
Agent, the catalyst 2 are catalytic cracking catalyst, and the catalytic cracking catalyst is using kaolin and montmorillonite as carrier, with cycloalkanes
Sour molybdenum and/or iron naphthenate are active component, and with the poidometer of catalytic cracking catalyst, kaolin and montmorillonite account for 37.5%-
87.5%, the mass ratio of kaolin and montmorillonite is 2.5-1:1, and molybdenum naphthenate and/or iron naphthenate account for 12.5%-62.5%.
2. application described in accordance with the claim 1, it is characterised in that in the catalytic cracking catalyst, with catalytic cracking catalyst
Poidometer, kaolin and montmorillonite account for 50%-70%, and the mass ratio of kaolin and montmorillonite is 2-1:1, molybdenum naphthenate and/
Or iron naphthenate accounts for 30%-50%.
3. application described in accordance with the claim 1, it is characterised in that the preparation method of the catalytic cracking catalyst, including with
Lower step:
1) kaolin and montmorillonite original powder are in 400-550 DEG C of roasting 2-10h；
2) kaolin obtained after step 1) roasting and montmorillonite are added in reactor, aphthenic acids is then added into reactor
The diluted acid maceration extract of iron and/or molybdenum naphthenate is impregnated；
3) material after step 2) reaction is dried under the conditions of 100-150 DEG C 2-6h, catalytic cracking catalyst is made.
4. application described in accordance with the claim 3, it is characterised in that step 1) uses the heating rate of 5-10 DEG C/min by kaolinite
Soil and montmorillonite original powder are warming up to maturing temperature.
5. application described in accordance with the claim 3, it is characterised in that step 2) is stirred while dipping, stirring rate 100-
150r/min, mixing time 0.5-2.5h.
6. application described in accordance with the claim 3, it is characterised in that diluted acid described in step 2) is in hydrochloric acid, nitric acid and acetic acid
It is at least one；In diluted acid maceration extract, the mass fraction of diluted acid is 5%-20%；Dipping described in step 2) is using supersaturation dipping
Method or saturation infusion process.
7. application described in accordance with the claim 1, it is characterised in that the usage amount of catalyst 1 is added waste plastics gross mass
5%-20%；The reaction condition of catalytic cracking reaction described in step (1) is as follows: reaction temperature is 350-550 DEG C, the reaction time
It is 30-150 minutes, reaction carries out under stiring, and stirring rate is 350-600 revs/min, needs to be passed through hydrogen, hydrogen in reaction
Partial pressure is 2-4MPa.
8. applying according to claim 7, it is characterised in that the usage amount of catalyst 1 is added waste plastics gross mass
10%-15%.
9. applying according to claim 7, 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；Reaction time is 45-120 minutes；Reaction carries out under stiring, stirring rate 400-
500 revs/min；Need to be passed through hydrogen, hydrogen partial pressure 2.5-3.5MPa in reaction.
10. application described in accordance with the claim 1, it is characterised in that the usage amount of catalyst 2 described in step (4) accounts for cellulose
The 2.5%-15% of quality；The sulphur that mass content is calculated as 4000-8000ppm with sulphur is added while catalyst 2 are added in step (4)
As vulcanizing agent, the mass ratio of sulfur content and iron and molybdenum total content is 5-7:1, selected sulphur source in source are as follows: sulphur, hydrogen sulfide,
One of carbon disulfide is a variety of.
11. application described in accordance with the claim 1, it is characterised in that the reaction condition of catalysis reaction described in step (4) is as follows:
Reaction temperature is 400-600 DEG C, and the reaction time is 30-100 minutes, and reaction carries out under stiring, stirring rate 350-600
Rev/min, need to be passed through hydrogen, hydrogen partial pressure 4-8MPa in reaction.
12. applying according to claim 11, it is characterised in that the reaction condition of catalysis reaction described in step (4) is such as
Under: reaction temperature is 450-550 DEG C；Reaction time is 60-100 minutes；Reaction carries out under stiring, stirring rate 400-
500 revs/min；Need to be passed through hydrogen, hydrogen partial pressure 5-6.5MPa in reaction.
13. according to application described in claim 11 or 12, it is characterised in that the reaction temperature ratio of step (4) the catalysis reaction
The reaction temperature of step (1) the catalysis reaction is at least 50 DEG C high, and the hydrogen partial pressure of step (4) the catalysis reaction is than step (1)
At least high 2MPa of the hydrogen partial pressure of the catalytic cracking reaction.
14. application described in accordance with the claim 1, it is characterised in that step (6) catalyst 3 is that phosphorus and tungsten are modified
HZSM-5 and HY composite molecular sieve catalyst, wherein the mass content of phosphorus is 1.5%-7.0%, and the mass content of tungsten is 0.3%-
2.0%.
15. according to application described in claim 1 or 14, it is characterised in that the usage amount of catalyst 3 is to be added to urge in step (6)
Change the 5%-18% of reaction mass gross mass added by the whole in reactor C.
16. applying according to claim 15, it is characterised in that the usage amount of catalyst 3 is that catalysis is added in step (6)
The 8%-13% of reaction mass gross mass added by whole in reactor C.
17. application according to claim 14, it is characterised in that catalyst 3 described in step (6) the preparation method comprises the following steps:
HZSM-5 and HY carries out being mixed to get composite molecular screen with mass ratio 0.5-2:1, and the phosphoric acid for being 10%-20% with mass concentration is molten
The mass ratio of liquid dipping composite molecular screen, phosphoric acid solution and composite molecular screen is 0.5-1:1, and dry 1-3 is small at 80-110 DEG C
When, then the sodium tungstate solution dipping composite molecular screen for being 1%-2% with mass concentration, the matter of sodium tungstate solution and composite molecular screen
Amount is 5-10 hours dry at 80-110 DEG C than being 0.5-1:1, then roasts 4-7 hours at 330-380 DEG C, after molding
To catalyst 3.
18. application described in accordance with the claim 1, it is characterised in that the reaction item of step (6) the Deep catalytic cracking reaction
Part are as follows: reaction temperature is 400-700 DEG C；Reaction time is 60-150 minutes；Reaction carries out under stiring, stirring rate 350-
600 revs/min；Need to be passed through hydrogen, hydrogen partial pressure 5-10MPa in reaction.
19. applying according to claim 18, it is characterised in that the reaction temperature of step (6) the Deep catalytic cracking reaction
Degree is 500-600 DEG C.
20. according to application described in claim 18 or 19, it is characterised in that step (6) the Deep catalytic cracking reaction it is anti-
Answer the reaction temperature of the temperature catalysis reaction more described than step (4) at least 50 DEG C high, step (6) the Deep catalytic cracking reaction
At least high 1MPa of hydrogen partial pressure of the hydrogen partial pressure catalysis reaction more described than step (4).
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| CN1462790A (en) * | 2003-05-26 | 2003-12-24 | 四川大学 | Catalyst for cracking waste plastics to generate fuel |
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