CN109876850A - A kind of preparation method of the composite molecular screen for bio oil deoxidation upgrading - Google Patents
A kind of preparation method of the composite molecular screen for bio oil deoxidation upgrading Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of composite molecular screen for bio oil deoxidation upgrading, step 1 takes concentrated hydrochloric acid to pour into adjust pH in the deionized water being ready for first, and the mass ratio of hydrochloric acid and water is 1:4~1:12.After mixing, micro porous molecular sieve HZSM-5 is added, using magnetic stirrer at suspension.It further weighs a certain amount of triblock copolymer template " polyethylene oxide-polypropylene oxide-polyethylene oxide P123 " and pours into suspension and quickly stir evenly, form colloidal solution.Silicon source ethyl orthosilicate is added into colloidal solution for step 2, quickly after stirring for 24 hours, is transferred to crystallization in the autoclave of tetrafluoroethene lining.Step 3 is opened after solution in reaction kettle is cooled to room temperature, by the gained filtration washing of solution containing crystal grain, and filtered crystal grain is placed in 120 DEG C of baking oven dry, Muffle furnace is used to rise to 550 DEG C with the heating rate of 10 DEG C/min again, 4h is roasted at 550 DEG C, Jie's mesoporous-microporous composite molecular sieve HZSM-5/SBA-15 with core-shell structure can be obtained.
Description
Technical field
The present invention relates to a kind of composite molecular screen preparation for bio oil deoxidation upgrading and optimization methods, mainly utilize
The structure and performance of regulation Jie's mesoporous-microporous composite molecular sieve produce hydrocarbon compound to be selectively pyrolyzed, and belong to biomass utilization skill
Art field.
Background technique
Biomass energy is that solar energy is changed into chemical energy by green plants photosynthesis and is stored up using biomass as carrier
There are the energy inside biomass, it is the fourth largest source for being only second to coal, petroleum, natural gas, the stock number of biomass is big,
It is one of the substitute of fossil fuel of most potential quality with reproducible ability is cleaned.
Pyrolysis is a kind of efficient biomass energy utilization technologies, biomass is converted to liquid biological oil by pyrolysis, both
Facilitate storage and transport, and energy density with higher.Biomass is directly pyrolyzed the bio oil of formation, and there is available hydrogen carbon
The problems such as relatively low, high oxygen content, calorific value are low, stability is poor.And a certain amount of catalyst is added in pyrolytic process can be with
Make have oxygen compound that the reaction such as dehydration, decarbonylation base, decarboxylation occurs in bio oil, the oxygen content in bio oil is reduced, to life
Object oil carries out deoxidation upgrading.
More micro porous molecular sieve HZSM-5 deoxidation with higher and aromatizing capacity are applied at present, it being capable of shape selective catalysis
Hydrocarbon out reduces the generation for having oxygen compound.But HZSM-5 cellular structure is smaller, is formed in biomass pyrolysis process
Macromolecular substances be difficult quickly to spread in duct, reduce the reaction rate of HZSM-5.And the surface HZSM-5 it is acid compared with
By force, it is easy to which coking and blocking causes molecular sieve to inactivate, and limits its application.Mesoporous molecular sieve SBA-15 is tied with good duct
Structure, the larger hole wall in aperture is thicker, and good hydrothermal stability, solid tumor speed is fast, but its weaker acidity makes its catalysis live
Property is not high.In view of the catalysis characteristics of micro porous molecular sieve HZSM-5 and mesoporous molecular sieve SBA-15 complementation, the present invention prepares one kind
Micro- mesoporous composite molecular sieve HZSM-5/SBA-15 with core-shell structure is relatively strong to obtain having by adjusting its preparation condition
The composite molecular screen of hydrocarbon selective.
Summary of the invention
Technical problem: it is an object of the present invention to provide a kind of composite molecular screen preparations and optimization for bio oil deoxidation upgrading
Method synthesizes the composite molecular screen HZSM-5/SBA-15 with core-shell structure using hydrothermal synthesis method, makes full use of micropore point
The advantage of son sieve HZSM-5 and mesoporous molecular sieve SBA-15 respectively, when by changing the pH in synthesis process, compositely proportional, crystallization
Between and crystallization temperature adjust the structural behaviour of molecular sieve, produce the composite molecular screen with stronger hydrocarbon selective.
Technical solution: in order to solve the above technical problems, a kind of compound molecule for bio oil deoxidation upgrading of the invention
The preparation method of sieve includes the following steps:
Step 1: taking concentrated hydrochloric acid to pour into first adjusts pH in the deionized water being ready for, after mixing, micropore is added
Molecular sieve HZSM-5, using magnetic stirrer at suspension；Further take triblock copolymer template " polycyclic oxygen second
Alkane-polypropylene oxide-polyethylene oxide P123 " is poured into above-mentioned suspension and is quickly stirred evenly, and forms colloidal solution；
Step 2: silicon source ethyl orthosilicate is added into above-mentioned colloidal solution, after stirring 18~32h, it is transferred to tetrafluoro second
Crystallization in the autoclave of alkene lining；Autoclave is placed in baking oven；
Step 3: taking out reaction kettle out of baking oven, opened after the reaction solution in reaction kettle is cooled to room temperature, by gained
Solution filtration washing containing crystal grain, and filtered crystal grain is placed in drying in 100~130 DEG C of baking oven, using Muffle furnace
500~600 DEG C are risen to the heating rate of 10 DEG C/min, it is lower at such a temperature to roast 2~6h, it can be obtained with core-shell structure
Jie's mesoporous-microporous composite molecular sieve HZSM-5/SBA-15.
Wherein:
Concentrated hydrochloric acid described in step 1 is the concentrated hydrochloric acid of 12mol/L.
Hydrochloric acid described in step 1 and the mass ratio of deionized water are 1:4~1:12.
Micro porous molecular sieve HZSM-5 described in step 1 and hydrochloric acid mass ratio are 1:4~1:10.
The mass ratio of template P123 and hydrochloric acid described in step 1 is 1:4~1:10.
The mass ratio of ethyl orthosilicate and hydrochloric acid is 1:2~1:4 in step 2, and whipping temp is 35 DEG C~60 DEG C, high pressure
Reaction kettle crystallization temperature is 90~120 DEG C, and crystallization time is 12~36h.
Autoclave is placed in baking oven in step 2,12~36h of crystallization under conditions of 90~120 DEG C.
Preferably 35~60 DEG C of whipping temp in step 1.
Silicon source and the preferred 1.5:1~2.5:1 of template mass ratio.
The utility model has the advantages that
1, change the biological oil quality of micropore and mesoporous composite quality than catalytic pyrolysis can be significantly improved.It is closed when being added
When the HZSM-5 of suitable content, the SBA-15 that follow-up hydrothermal can be made to synthesize just completely is attached to the surface of HZSM-5, is formed
The core-shell structure completely coated.Complete core-shell structure can make all pyrolysis gas that can first pass through mesoporous SBA-15 sufficiently to urge
Change, enters back into HZSM-5 and complete deoxidation aromatisation, HZSM-5 and SBA-15 have the function that concerted catalysis.
2, the cellular structure and skeleton hydrothermal stability of molecular sieve can be adjusted by changing crystallization time and crystallization temperature,
Skeleton stability height can be generated in suitable crystallization time and crystallization temperature, and the good composite molecular screen of cellular structure is conducive to
The catalysis and diffusion of molecule, preferable hydrothermal stability also extend the service life of molecular sieve in pyrolytic process.
3, the composite molecular screen is applied in biomass or catalytic lignin pyrolytic reaction, and pyrolysis gas can preferentially pass through " shell "
Larger molecular organics are resolved into small point by its excellent duct characteristic and mesoporous characteristic by the SBA-15 mesopore molecular sieve of structure
Sub- organic matter, small organic molecule select type deoxidation and aromatisation by it using the HZSM-5 micro porous molecular sieve of " core " structure
Ability form the high added values organic matter such as hydro carbons.Due to the cladding of SBA-15, the acidic site on the surface HZSM-5 is partially covered
Lid, carbon deposition rate decline, molecular sieve coking and deactivation rate significantly reduce.
Detailed description of the invention
Fig. 1 is HZSM-5/SBA-15 composite molecular screen preparation flow figure.
Fig. 2 is bamboo and wood non-catalytic pyrolysis and addition HZSM-5/SBA-15 composite molecular screen thermal decomposition product distribution.
Fig. 3 is the composite molecular screen catalytic pyrolysis product distribution of bamboo and wood addition different composite ratio.
Specific embodiment
Below in conjunction with attached drawing, technical scheme is described further, but the scope of protection of present invention is simultaneously
It is not limited to this.
The present invention provides a kind of composite molecular screen preparation for bio oil deoxidation upgrading and optimization method.It is de- to choose catalysis
Oxygen and the good HZSM-5 micro porous molecular sieve of aromatization effect and duct is excellent, SBA- of large specific surface area, good hydrothermal stability
15 mesopore molecular sieves.SBA-15 is added on the surface HZSM-5 with hydrothermal synthesis method, forming inner core is HZSM-5, and external shell is
The composite molecular screen of SBA-15.When carrying out catalytic pyrolysis to biomass with the molecular sieve, it is preliminary that pyrolysis gas can first pass through SBA-15
Cracking, then further refined by HZSM-5.By changing hydrochloric acid additive amount, molecular sieve composite quality ratio, crystalline substance in synthesis process
Change Jie's mesoporous-microporous composite molecular sieve of time and the adjustable best catalytic effect out of crystallization temperature.The composite molecular screen is selected with hydro carbons
Selecting property height, large specific surface area, hydrothermal stability be strong and the remarkable advantages such as long service life.
The present invention includes the following steps:
Step 1: a certain amount of deionized water is added in beaker, then weighs the concentrated hydrochloric acid of 12mol/L and be added to deionization
In water, it is placed on magnetic stirring apparatus at 35~60 DEG C and is sufficiently stirred.After 1h, weighs HZSM-5 molecular sieve powder and be added to solution
In quickly stir, formed suspension.It weighs triblock copolymer template P123 and is added in suspension and 2h is sufficiently stirred is formed
Colloidal solution makes template be attached to the surface of HZSM-5.
Step 2: silicon source ethyl orthosilicate (TEOS) is added in the colloidal solution that step 1 stirs evenly, at 40 DEG C
It tunes up revolving speed and is vigorously stirred 18~32h, so that TEOS is fully hydrolyzed and is attached on template.The solution after stirring is moved to again
In the autoclave of tetrafluoroethene lining, autoclave is placed in baking oven, under conditions of 90~130 DEG C crystallization 12~
36h。
Step 3: taking out reaction kettle, the opening when solution in reaction kettle is cooled to room temperature, the solution by gained containing crystal grain
Filtration washing, and filtered crystal grain is placed in dry 2h in 100~130 DEG C of baking oven.Molecular sieve after drying is put into
In Muffle furnace, Muffle furnace is risen to 550 DEG C with the heating rate of 10 DEG C/min, and roasts 2~6h at 550 DEG C to remove removing template
Agent obtains Jie's mesoporous-microporous composite molecular sieve with core-shell structure.
In the present invention, hydrochloric acid and deionized water are preferably in a proportion of 1:12~1:3, most preferred ratio 1:6.Whipping temp
It is preferred that 35~60 DEG C, more preferable 38~42 DEG C, most preferably 40 DEG C.HZSM-5 and hydrochloric acid are preferably in a proportion of 1:4~1:10, most preferably
1:8.Template and hydrochloric acid are preferably in a proportion of 1:4~1:10, most preferably 1:5.Silicon source and the preferred 1.5:1 of template mass ratio~
2.5:1 most preferably 2:1.Preferably 90~130 DEG C of crystallization temperature, preferably temperature is 100 DEG C, crystallization time preferably 12~
36h, most preferably time are for 24 hours.
Micro- mesoporous composite molecular sieve preparation method in the present invention is as shown in Figure 1, include the following steps:
Step 1: a certain amount of deionized water is added in beaker, then weigh a certain amount of (with water quality ratio 1:6) 12mol/
The concentrated hydrochloric acid of L is add to deionized water, and is placed on magnetic stirring apparatus at 40 DEG C and is sufficiently stirred.After 1h, HZSM-5 points are weighed
Son sieve powder (with hydrochloric acid mass ratio 1:8) is added in solution and quickly stirs, and stirs and stops when solution is remained without obvious powder.
It weighs triblock copolymer template P123 (with hydrochloric acid mass ratio 1:5) and is added in solution and 2h is sufficiently stirred, keep template attached
On the surface of HZSM-5.
Step 2: a certain amount of silicon source ethyl orthosilicate TEOS is added in the solution that step 1 stirs evenly (with template
Mass ratio 2:1), revolving speed is tuned up at 40 DEG C and is vigorously stirred for 24 hours, so that TEOS is fully hydrolyzed and is attached on template.Again will
Solution after stirring moves in the autoclave of tetrafluoroethene lining, and autoclave is placed in baking oven, in 100 DEG C of item
Crystallization is for 24 hours under part.
Step 3: taking out reaction kettle, acquired solution is crossed diafiltration by the opening when solution in reaction kettle is cooled to room temperature
It washs, and is placed in 120 DEG C of baking oven dry 2h.Molecular sieve after drying is put into Muffle furnace, with the heating of 10 DEG C/min
Muffle furnace is risen to 550 DEG C by rate, and roasts 4h at 550 DEG C to remove template agent removing, obtains Jie's micropore with core-shell structure
Composite molecular screen.
Embodiment 1
Catalytic pyrolysis test is carried out to bamboo and wood using the composite molecular screen that most preferably scheme is prepared, using thermal cracking-
Gc/ms Analyser (Py/GC-MS) reaction unit, to compare non-catalytic pyrolysis, HZSM-5 catalytic pyrolysis and HZSM-
The product of 5/SBA-15 composite molecular screen catalytic pyrolysis is distributed.
Biomass chooses bamboo and wood, and son is sieved with 100 mesh sieve before experiment and dries preservation.Used in the dress sample of bamboo and wood non-catalytic pyrolysis
Quartzy bore 1.9mm, length 25mm are adopted and are weighed the bamboo and wood of 0.5mg in the balance and be added in pipe with pan paper, and both sides use stone
English cotton is from left to right followed successively by silica wool, bamboo and wood, silica wool to fixed bamboo and wood.When adding composite molecular screen, from left to right
It is followed successively by silica wool, molecular sieve, silica wool, bamboo and wood, silica wool, molecular sieve, silica wool.Catalytic pyrolysis temperature is 600 DEG C, program
Heating rate is 20 DEG C/ms, and the catalytic pyrolysis time is 3s.
Use National Institute of Standards and Technology (National Institute of Standards and
Technology, NIST) database is to the product progress qualitative analysis after pyrolysis, using area normalization method come the gas phase to product
Chromatograph-mass spectrometer spectrogram (GC/MS) carries out quantitative analysis.Bamboo and wood non-catalytic pyrolysis and the production that molecular sieve catalytic pyrolysis is added
Object distribution is as shown in Figure 2.In the case where not adding catalyst, pyrolysis has mainly generated oxygen compound, almost without hydrocarbons
It generates.After HZSM-5 micro porous molecular sieve is added, hydro carbons yield is significantly improved.When use microporous mesoporous compositely proportional for 2:1's
When HZSM-5/SBA-15, can than be used alone HZSM-5 more efficiently output hydro carbons, yield reach 53%.Know preparation
Composite molecular screen can effectively improve hydrocarbons yield, promote the raising of quality of bio-oil.
Embodiment 2
For the catalytic effect of composite molecular screen under more different mesoporous micropore compositely proportionals, using HZSM-5:SBA-15=
Tri- kinds of composite molecular screens of 1:2,1.25:1 and 2:1 test bamboo and wood catalytic pyrolysis using Py/GC-MS device.Biomass choosing
Bamboo and wood is taken, the bamboo and wood of 0.5mg is weighed, is added in pipe with pan paper, both sides are packed into silica wool and are fixed, and respectively fill then at both ends
The HZSM-5/SBA-15 composite molecular screen for entering 0.5mg different composite ratio, is finally fixed with silica wool.Catalytic pyrolysis temperature is
600 DEG C, programmed rate is 20 DEG C/ms, and the catalytic pyrolysis time is 3s.
Qualitative analysis is carried out to thermal decomposition product using NIST database, product distribution is as shown in Figure 3.With micro- in molecular sieve
The increase of hole proportion, the hydro carbons that catalytic pyrolysis is formed first gradually increases, and the hydro carbons in HZSM-5:SBA-15=1.25:1
Yield reaches peak 57.1%.Molecular sieve at this time make all pyrolysis gas can be transferred through mesoporous SBA-15 it is sufficiently catalytic after,
The process of deoxidation aromatisation is completed into HZSM-5, HZSM-5 and SBA-15 have the function that concerted catalysis.Shared by HZSM-5
After ratio continues growing, synergistic effect weakens, and gradually approaches the effect of HZSM-5 single-stage catalytic pyrolysis.It knows by changing micropore
With the adjustable catalyst performance of mesoporous ratio so that hydrocarbon selective is more prominent.
Claims (9)
1. a kind of preparation method of the composite molecular screen for bio oil deoxidation upgrading, which is characterized in that the preparation method includes
Following steps:
Step 1: taking concentrated hydrochloric acid to pour into first adjusts pH in the deionized water being ready for, after mixing, microporous molecular is added
HZSM-5 is sieved, using magnetic stirrer at suspension；Further taking triblock copolymer template, " polyethylene oxide-is poly-
Propylene oxide-polyethylene oxide P123 " is poured into above-mentioned suspension and is quickly stirred evenly, and forms colloidal solution；
Step 2: silicon source ethyl orthosilicate is added into above-mentioned colloidal solution, after stirring 18~32h, it is transferred to tetrafluoroethene lining
In autoclave in, autoclave is placed in baking oven, makes internal colloidal solution crystallization for a period of time；
Step 3: taking out reaction kettle out of baking oven, opened after the reaction solution in reaction kettle is cooled to room temperature, by gained containing crystalline substance
The solution filtration washing of grain, and filtered crystal grain is placed in drying in 100~130 DEG C of baking oven, use Muffle furnace with 10
DEG C/heating rate of min rises to 500~600 DEG C, and it is lower at such a temperature to roast 2~6h, Jie with core-shell structure can be obtained
Mesoporous-microporous composite molecular sieve HZSM-5/SBA-15.
2. the preparation method of the composite molecular screen according to claim 1 for bio oil deoxidation upgrading, which is characterized in that
Concentrated hydrochloric acid described in step 1 is the concentrated hydrochloric acid of 12mol/L.
3. the preparation method of the composite molecular screen according to claim 1 or 2 for bio oil deoxidation upgrading, feature exist
In the mass ratio of hydrochloric acid described in step 1 and deionized water is 1:4~1:12.
4. the preparation method of the composite molecular screen according to claim 1 or 2 for bio oil deoxidation upgrading, feature exist
In micro porous molecular sieve HZSM-5 described in step 1 and hydrochloric acid mass ratio are 1:4~1:10.
5. the preparation method of the composite molecular screen according to claim 1 or 2 for bio oil deoxidation upgrading, feature exist
In the mass ratio of template P123 and hydrochloric acid described in step 1 is 1:4~1:10.
6. the preparation method of the composite molecular screen according to claim 1 or 2 for bio oil deoxidation upgrading, feature exist
In the mass ratio of ethyl orthosilicate and hydrochloric acid is 1:2~1:4 in step 2, and whipping temp is 35 DEG C~60 DEG C, autoclave
Crystallization temperature is 90~120 DEG C, and crystallization time is 12~36h.
7. the preparation method of the composite molecular screen according to claim 1 for bio oil deoxidation upgrading, which is characterized in that
Autoclave is placed in baking oven in step 2,12~36h of crystallization under conditions of 90~120 DEG C.
8. the preparation method of the composite molecular screen according to claim 1 for bio oil deoxidation upgrading, which is characterized in that
Preferably 35~60 DEG C of whipping temp in step 1.
9. the preparation method of the composite molecular screen according to claim 1 for bio oil deoxidation upgrading, which is characterized in that
Silicon source and the preferred 1.5:1~2.5:1 of template mass ratio.
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Application publication date: 20190614 |
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