CN105217649B - A kind of method of two steps in low temperature removing organic formwork agent and the device for realizing this method - Google Patents
A kind of method of two steps in low temperature removing organic formwork agent and the device for realizing this method Download PDFInfo
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- CN105217649B CN105217649B CN201510708752.8A CN201510708752A CN105217649B CN 105217649 B CN105217649 B CN 105217649B CN 201510708752 A CN201510708752 A CN 201510708752A CN 105217649 B CN105217649 B CN 105217649B
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Abstract
The present invention relates to a kind of method that two steps in low temperature removes organic formwork agent, comprise the following steps：1) the high silicon porous material containing organic formwork agent is positioned in atmosphere furnace, will be vacuumized in atmosphere furnace, led to hydrogen to normal pressure, rise to 300~350 DEG C with 1.0~10 DEG C/min heating rates, constant temperature makes organic formwork agent fully decompose；2) keep step 1 thermostat temperature constant, vacuumized in stove, open air adjustment valve, be passed through air to normal pressure, air constant temperature oxidation processing is carried out to high silicon porous material；3) 0~0.1m is maintained3/ h air velocity, terminates the heating schedule of atmosphere furnace, is naturally cooling to normal temperature, closes the seal assembly that air control valve opens atmosphere furnace, obtains the high silicon porous material without organic formwork agent.Present invention process mild condition, simple to operate, with low cost, applicability are wide, not only contribute to the planningization production of high silicon porous material, and are conducive to the industrialization of porous, inorganic membrane separation technique.
Description
Technical field
The invention belongs to inorganic porous material and adsorption separation technology field, and in particular to a kind of two steps in low temperature removing has
The method of machine template and the device for realizing this method.
Background technology
In recent years, high silicon porous material is due to larger specific surface area, the homogeneous and continuously adjustabe on nano-scale
Regular pore passage structure, surface group is functionalisable etc., and series of advantages receives extensive concern, as catalysis and separation material
The study hotspot in field.Research is found, is fettered characteristic using the geometry and electronics in high silicon porous material duct, can be reached stabilization
The purpose of Nanoparticle shape, structure and electronic property, can provide carrier-mediated catalysis to construct the catalyst of low temperature high activity
Agent provides carrier.High-silica zeolite particle in high silicon porous material, which can also be cross-linked with each other, is grown to serve as the high silicon molecule of densification
Sieve membrane, it has regular pore passage structure, good chemical stability, mechanical strength, heat endurance and catalytic performance, in film point
There is potential application value from fields such as technology and membrane catalytic reactions, the extensive concern of researchers is also result in.
Need to add organic formwork agent mostly when preparing synthesizing high-silicon porous material, to be formed with special duct knot
The porous material of structure；Using it is preceding and need by high-temperature calcination technique remove organic formwork agent, to make duct result unimpeded.
However, due to the difference of thermal expansion direction and amplitude between porous material itself different orientation, and porous material and support carrier
Between hot expansion property difference so that high silicon porous material forms skeleton because of thermal stress and collapsed and the intergranular such as crackle at high temperature
Defect, these defects can significantly reduce its catalytic separation characteristic.Thus, how to be prevented effectively from and remove organic formwork agent in heat treatment
When the intergranular defect that is formed turned into a severe challenge for restricting high silicon porous material preparation and application technology development.Research knot
Fruit finds, when reducing the calcining heat of template to less than 350 DEG C, is conducive to keeping the regular duct of high silicon porous material to tie
Structure.
In recent years, low temperature removed studying for organic formwork agent in high silicon porous material turns into the focus of many focus of attention
Problem.The method of existing low temperature removing organic formwork agent mainly includes two classes：One kind is by using strong oxidizer oxidation removal
The template of high silicon porous material, its oxidant species include ozone, hydrogen peroxide and potassium permanganate etc.；Another is by physics
Chemical method carrys out removed template method, removes high silicon using technologies such as solvent extraction, microwave, overcritical and cold plasmas porous
Material internal mold plate agent.But, this more two classes method is to be directed to high silicon mesoporous material, such as SBA-15 and MCM-41；And for
Using more high silicon poromerics, but because template and cell walls adhesion hand over strong, and it is caused still to be difficult to have at low temperature
Effect removing organic formwork agent.In addition, these above-mentioned existing low temperature removed template method techniques are typically necessary special instrument and set
Standby, its operating procedure is also complex, therefore urgently develops a kind of high efficient cryogenic suitable for the high silicon porous material of different pore size
Remove the technique and equipment of organic formwork agent.
The content of the invention
It is an object of the present invention to provide a kind of method that two steps in low temperature removes organic formwork agent, it uses low temperature
The method of hydrocracking and air constant temperature oxidation removes organic formwork agent, and this method overcomes existing high silicon porous material to prepare work
The technical bottleneck of low temperature removing organic formwork agent is gentle there is provided a kind of process conditions in skill, the simple and with low cost mould of process
Plate agent low temperature removing process.
In order to realize foregoing invention purpose, technical scheme is as follows：
A kind of method that two steps in low temperature removes organic formwork agent, it is characterised in that comprise the following steps：
1) first the high silicon porous material containing organic formwork agent is positioned in atmosphere furnace, then will takes out true in the atmosphere furnace
Sky, is slowly introducing after hydrogen to normal pressure, and 300~350 DEG C are risen to 1.0~10 DEG C/min heating rates, and constant temperature makes organic mould
Plate agent is fully decomposed；
2) after the step (1) completes, keep step 1 thermostat temperature constant, then will be vacuumized in stove, then open empty
Gas control valve, is slowly introducing after dry air to normal pressure, and air constant temperature oxidation processing is carried out to the high silicon porous material；
3) 0~0.1m is maintained3/ h constant air flow velocity, terminates the heating schedule of atmosphere furnace, it is naturally cooling to often
Temperature, is then shut off air control valve and opens the seal assembly of atmosphere furnace, finally gives the high silicon without organic formwork agent porous
Material.
The present invention creatively organically combines low temperature hydrogenation cracking technique and low temperature air oxidation technology, preferably
Solve organic formwork agent in high silicon porous material efficient cryogenic removing problem.Made using low temperature hydrogenation cracking technology porous
Most of organic formwork agent in material resolves into small organic molecule, so that cell channels are opened, is forged using Cryogenic air
Firing technique makes remaining lacking in porous material stay organic formwork agent fully to be contacted with air and complete oxidation, finally realizes porous material
The complete removing of organic formwork agent in material.
Preferably, the high silicon porous material in the step 1 has the orderly pore passage structure that aperture is 0.3~30 nanometer,
Including silicon, oxygen and aluminium element, the wherein mol ratio of element silicon and aluminium element is more than 50.
Preferably, the high silicon porous material is sieve particle or molecular screen membrane.High-silica zeolite porous material has many
Kind, in the present invention from the maximum SBA-15 types molecular sieve in aperture, aperture high silicon MCM-41 types molecular sieve placed in the middle and aperture most
Small high silicon MFI-type molecular sieve.
Preferably, hydrogen flow rate is 0.1~0.5m in 10~20h of constant temperature in the step 1, thermostatic process3/h。
Preferably, 10~20h of constant temperature in the step 2, air velocity is 0.1~0.5m3/h。
Preferably, the constant temperature time of 300 DEG C of processing is 20h, the constant temperature time of 350 DEG C of processing in the step 1 and step 2
For 10h.
Preferably, the hydrogen volume concentration in the step 1 in atmosphere furnace is not less than 50.0%.
Preferably it is not less than 60.0%, hydrogen there is provided the hydrogen volume concentration in the hydrogen-holder of hydrogen described in step 1
Gas pressure in storage tank is not less than 0.5MPa.
It is another object of the present invention to provide a kind of dress for the method for realizing two steps in low temperature removing organic formwork agent
Put, the device is simple, it is easy to large-scale production.
The invention provides it is a kind of realize two steps in low temperature removing organic formwork agent method device, including atmosphere furnace,
Air compressor, hydrogen cooler and the low pressure hydrogen storage tank being connected with the atmosphere furnace by pipeline, the hydrogen cooler
It is connected with low pressure hydrogen circulating pump, the low pressure hydrogen storage tank is connected with hydrogen membrane separation plant.
Preferably, in addition to tail gas burning furnace, the tail gas burning furnace is connected with the hydrogen membrane separation plant.
The present invention technical process be：
Removed enabling equipment low temperature in high silicon porous material before organic formwork agent, pure hydrogen is first supplemented into hydrogen-holder
Gas, makes the gas pressure in hydrogen-holder reach 0.5~1.0MPa；Atmosphere furnace is sealed at normal temperatures and vacuumized de- simultaneously
Gas；When carrying out low temperature Template removal, hydrogen-rich gas is passed through by hydrogen regulating valve with constant flow rate by atmosphere furnace bottom, through height
After silicon porous material, from the discharge of atmosphere furnace top, after hydrogen cooler, recycled into hydrogen-holder；Complete once
After the operation of low temperature hydrogenation cracking removing organic formwork agent, again atmosphere furnace is carried out vacuumizing degassing and open air compression
Machine, then carries out the operation of a low temperature air oxidation removing organic formwork agent, dry air is by air control valve with perseverance again
Constant current speed is passed through by atmosphere furnace bottom, through after high silicon porous material, from the emptying of atmosphere furnace top；Finally, atmosphere furnace is closed
Temperature control program simultaneously turns air mass flow down, makes after it is naturally cooling to below 30 DEG C of normal temperature, to close air control valve and simultaneously open atmosphere
The seal assembly of stove, finally gives clean and flawless high silicon porous material.During whole low temperature removing organic formwork agent,
Hydrogen volume concentration in atmosphere furnace maintains 50.0~99.0%；When the hydrogen volume concentration in hydrogen-holder is less than 60.0%
When, batch (-type) opens the density of hydrogen that hydrogen membrane separation plant comes in raising system, until the hydrogen volume in hydrogen-holder is dense
Degree reaches 90.0%；When the gas pressure in hydrogen-holder is less than 0.5MPa, it is necessary to supplement pure hydrogen gas (purity>
99.0%), up to the gas pressure in hydrogen-holder>0.75MPa；The tail gas of hydrogen membrane separation plant discharge, is passed through tail gas and burns
Burn stove and carry out innoxious burning processing, the heat smoke of incinerator discharge enters flue gas heat-exchange unit, recovery waste heat by utilidor
After empty.
The beneficial effects of the invention are as follows：
(1) using low temperature hydrogenation cracking technology, most of organic formwork agent in porous material is resolved into small molecule organic
Thing, so that cell channels are opened；
(2) remaining lacking in porous material is made to stay organic formwork agent abundant with air using low temperature air oxidation calcine technology
Contact and complete oxidation, finally realize the complete removing of organic formwork agent in porous material；
(3) present invention process mild condition, operate that more simple, cost is more cheap, applicability is wider, not only contribute to
The planningization production of high silicon porous material, and be conducive to the industrialization of porous, inorganic membrane separation technique.
Brief description of the drawings
Accompanying drawing 1 removes organic formwork agent process chart for the two steps in low temperature of the present invention；
Accompanying drawing 2 is to remove high silicon SBA-15 type molecular sieves under the different heating rates of the embodiment of the present invention 1~4 and air velocity
The thermogravimetric curve figure of particle, wherein (a) for containing organic formwork agent molecular sieve as former state, (b) be heating rate be 10 DEG C/min and
Air velocity is 0.1m3Sample after/h removed template methods, (c) is that heating rate is 10 DEG C/min and air velocity is 0.5m3/h
Sample after removed template method, (d) is that heating rate is 5.0 DEG C/min and air velocity is 0.1m3After/h removed template methods
Sample, (e) is that heating rate is 5.0 DEG C/min and air velocity is 0.5m3Sample after/h removed template methods, (f) is 500 DEG C
Sample after conventional high-temperature calcining removed template method；
Accompanying drawing 3A and 3B are to remove high silicon MCM-41 types under the different hydrogen concentration of the embodiment of the present invention 5~7 and hydrogen flow rate
The infrared spectrum of molecular screen membrane, wherein (a) is the molecular sieve former state containing organic formwork agent, (b) is density of hydrogen 90% and hydrogen
Flow velocity is 0.5m3Sample after/h removed template methods, (c) is density of hydrogen 90% and hydrogen flow rate is 0.1m3/ h removed template methods
Sample afterwards, (d) is density of hydrogen 50% and hydrogen flow rate is 0.5m3Sample after/h removed template methods, (e) is 500 DEG C of biographies
Sample after system high-temperature calcination removed template method；
Accompanying drawing 4 is to remove high silicon MFI-type molecular sieve particle under the different temperatures of the embodiment of the present invention 8~10 and constant temperature time
Raman spectrogram, wherein (a) is the molecular sieve former state containing organic formwork agent, after (b) is constant temperature 20h removed template method at 300 DEG C
Sample, (c) is the sample after constant temperature 10h removed template methods at 300 DEG C, after (d) is constant temperature 10h removed template method at 350 DEG C
Sample, (e) is the sample after 500 DEG C of conventional high-temperature calcining removed template methods；
Accompanying drawing 5 is the Raman spectrogram that high silicon MFI-type molecular screen membrane is removed under the conditions of the different operating of the embodiment of the present invention 11, its
Middle diaphragm M3-1Result is cracked for low temperature hydrogenation, wherein diaphragm M3-2For low temperature air oxidation result, wherein diaphragm M3-3For tradition
High-temperature calcination result；
Accompanying drawing 6 is the CO that high silicon MFI-type molecular screen membrane is removed under the conditions of the different operating of the embodiment of the present invention 112/N2Separation effect
Really, wherein diaphragm M3-1Result is cracked for low temperature hydrogenation, wherein diaphragm M3-2For low temperature air oxidation result, wherein diaphragm M3-3
For conventional high-temperature results for calcination；
Description of reference numerals：1st, temperature programming atmosphere furnace, 2, air compressor, 3, hydrogen cooler, 4, low pressure hydrogen follows
Ring pump, 5, low pressure hydrogen storage tank, 6, hydrogen membrane separation plant, 7, tail gas burning furnace.
Embodiment
With reference to instantiation, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Technical staff makes according to the present invention in actual applications improvement and tune
It is whole, still fall within protection scope of the present invention.
The equipment and reagent used except special instruction, the present invention is the conventional commercial products of the art, and the present invention is used
Method be the conventional use of method of the art.Normal temperature and pressure is in the present invention：Temperature is 25 degree, and normal pressure is
0.1MPa.The direction of arrow is the flow direction of gas in Fig. 1.
High-silica zeolite porous material has a variety of, is occupied in the present invention from the maximum SBA-15 types molecular sieve in aperture, aperture
In the minimum high silicon MFI-type molecular sieve of high silicon MCM-41 types molecular sieve and aperture.Wherein SBA-15 types molecular sieve, high silicon MCM-
41 type molecular sieves and high silicon MFI-type molecular sieve are purchased from catalysis factory of Nankai University.
Infrared detection is carried out using the TENSOR27 FTISs of German Bruker companies, using France
The LabRAM HR800-LS55 type FT-Raman and confocal Ramans instrument of Horiba Jobin Yvon companies carries out Raman spectrum inspection
Survey.
Embodiment 1
Referring to shown in Fig. 1 and Fig. 2：
The present invention technical process be：
Remove in high silicon porous material before organic formwork agent, first mended into low pressure hydrogen storage tank 5 enabling equipment low temperature
Pure hydrogen gas is filled, the gas pressure in low pressure hydrogen storage tank 5 is reached 0.5~1.0MPa；Temperature programmed control atmosphere furnace 1 is existed simultaneously
Sealed under normal temperature and vacuumize degassing；Carry out low temperature Template removal when, hydrogen-rich gas by hydrogen regulating valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the discharge of temperature programmed control atmosphere furnace top, passes through hydrogen
After cooler 3 and low pressure hydrogen circulating pump 4, recycled into low pressure hydrogen storage tank 5；Complete a low temperature hydrogenation cracking removing
After the operation of organic formwork agent, again temperature programmed control atmosphere furnace 1 is carried out vacuumizing degassing and open air compressor 2, then
Carry out the operation that low temperature air oxidation removes organic formwork agent again, dry air by air control valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the emptying of the top of temperature programmed control atmosphere furnace 1；Finally, close
Close the temperature control program of temperature programmed control atmosphere furnace 1 and turn air mass flow down, make after it is naturally cooling to below 30 DEG C of normal temperature, to close empty
Gas regulating valve and the seal assembly for opening atmosphere furnace, finally give clean and flawless high silicon porous material.Whole low temperature takes off
During organic formwork agent, the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0~99.0%；Work as pressure hydrogen
When hydrogen volume concentration in gas storage tank 5 is less than 60.0%, batch (-type) opens the hydrogen that hydrogen membrane separation plant 6 comes in raising system
Gas concentration, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%；When the gas pressure in low pressure hydrogen storage tank 5
Power be less than 0.5MPa when, it is necessary to supplement pure hydrogen gas (purity>99.0%), up to the gas pressure in low pressure hydrogen storage tank 5>
0.75MPa；The tail gas that hydrogen membrane separation plant 6 is discharged, is passed through tail gas burning furnace 7 and carries out innoxious burning processing, burn fire grate
The heat smoke gone out, is entered after flue gas heat-exchange unit, recovery waste heat by utilidor and emptied.
A kind of method that two steps in low temperature removes organic formwork agent, comprises the following steps：
(1) organic formwork agent in the high silicon SBA-15 type molecular sieves of low temperature hydrogenation cracking removing
The aperture containing organic formwork agent purchased first is placed in program for 15~30nm high silicon SBA-15 type sieve samples
In temperature control atmosphere furnace, vacuum then will be evacuated in atmosphere furnace for -0.09MPa, then is slowly introducing after hydrogen to normal pressure, with 10
DEG C/min heating rates rise to 300 DEG C, constant temperature 20h is naturally cooling to room temperature, and hydrogen flow rate is 0.1m during this3/h。
(2) two steps in low temperature removes organic formwork agent in high silicon SBA-15 type molecular sieves
By keeping, the sample in step 1 after hydrocracking process removed template method is constant, again by temperature programmed control atmosphere furnace
Vacuum is evacuated to, then is slowly introducing after air to normal pressure, room temperature is naturally cooling to after constant temperature 20h again at 300 DEG C, is taken out；This
During air velocity be 0.1m3/h。
(3) 0~0.1m is maintained3/ h constant air flow velocity, terminates the heating schedule of atmosphere furnace, it is naturally cooling to often
Less than 30 DEG C of temperature, is then shut off air control valve and opens the seal assembly of atmosphere furnace, finally give without organic formwork agent
Molecular screen material.
Atmosphere furnace uses temperature programmed control atmosphere furnace in the present embodiment, but the atmosphere furnace of the present invention is not limited to only use
Temperature programmed control atmosphere furnace, other have the atmosphere furnace of identical function within protection scope of the present invention.In the present embodiment step 1
Middle that -0.09MPa will be evacuated in atmosphere furnace, the pressure limit that the present invention is vacuumized is not limited to -0.09MPa, this area
Technical staff it is conceivable that pressure limit within protection scope of the present invention.
Embodiment 2
Same as Example 1, difference is：
Air velocity is 0.5m3/h。
Embodiment 3
Same as Example 1, difference is：
Heating rate is 5.0 DEG C/min.
Embodiment 4
Same as Example 2, difference is：
Heating rate is 5.0 DEG C/min, and air velocity is 0.5m3/h。
Comparative example 1
Conventional high-temperature calcination method removes organic formwork agent in high silicon SBA-15 type molecular sieves
By molecular sieve powder sample as in Muffle furnace, 500 DEG C are risen to 1 DEG C/min heating rates, constant temperature 10h is natural
Room temperature is cooled to, obtained molecular screen material is taken out.
Molecular screen material made from high silicon SBA-15 types sieve sample, embodiment 1~4 and comparative example 1 is carried out respectively
Thermogravimetric is detected：
Enter thermogravimetric to sieve sample using the STA409C synthesis thermal analyzers of German Netzsch companies to characterize, the equipment
Operating condition is：Air is carrier gas, is warming up to 800 DEG C with 20 DEG C/min speed, accompanying drawing 2 is its testing result.
It can be drawn by Fig. 2, the effect of conventional high-temperature calcine technology is fully achieved using two steps in low temperature removing process,
But heat treatment temperature can drop to 300 DEG C by 500 DEG C, and its result shows, heating rate and air velocity have to low temperature removing
The effect of machine template also has certain influence, and heating rate is more low better, and the higher the better for air velocity.For tested high silicon
SBA-15 type molecular sieve powder samples, the effect of embodiment 4 is best, therefore optimum operation condition is：Heating rate be 5.0 DEG C/
Min and air velocity are 0.5m3/h。
Embodiment 5
Referring to shown in Fig. 1, Fig. 3 A and Fig. 3 B：
The present invention technical process be：
Remove in high silicon porous material before organic formwork agent, first mended into low pressure hydrogen storage tank 5 enabling equipment low temperature
Pure hydrogen gas is filled, the gas pressure in low pressure hydrogen storage tank 5 is reached 0.5~1.0MPa；Temperature programmed control atmosphere furnace 1 is existed simultaneously
Sealed under normal temperature and vacuumize degassing；Carry out low temperature Template removal when, hydrogen-rich gas by hydrogen regulating valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the discharge of temperature programmed control atmosphere furnace top, passes through hydrogen
After cooler 3 and low pressure hydrogen circulating pump 4, recycled into low pressure hydrogen storage tank 5；Complete a low temperature hydrogenation cracking removing
After the operation of organic formwork agent, again temperature programmed control atmosphere furnace 1 is carried out vacuumizing degassing and open air compressor 2, then
Carry out the operation that low temperature air oxidation removes organic formwork agent again, dry air by air control valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the emptying of the top of temperature programmed control atmosphere furnace 1；Finally, close
Close the temperature control program of temperature programmed control atmosphere furnace 1 and turn air mass flow down, make after it is naturally cooling to below 30 DEG C of normal temperature, to close empty
Gas regulating valve and the seal assembly for opening atmosphere furnace, finally give clean and flawless high silicon porous material.Whole low temperature takes off
During organic formwork agent, the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0~99.0%；Work as pressure hydrogen
When hydrogen volume concentration in gas storage tank 5 is less than 60.0%, batch (-type) opens the hydrogen that hydrogen membrane separation plant 6 comes in raising system
Gas concentration, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%；When the gas pressure in low pressure hydrogen storage tank 5
Power be less than 0.5MPa when, it is necessary to supplement pure hydrogen gas (purity>99.0%), up to the gas pressure in low pressure hydrogen storage tank 5>
0.75MPa；The tail gas that hydrogen membrane separation plant 6 is discharged, is passed through tail gas burning furnace 7 and carries out innoxious burning processing, burn fire grate
The heat smoke gone out, is entered after flue gas heat-exchange unit, recovery waste heat by utilidor and emptied.
A kind of method that two steps in low temperature removes organic formwork agent, comprises the following steps：
(1) organic formwork agent in the high silicon MCM-41 type molecular sieves of low temperature hydrogenation cracking removing
The aperture containing organic formwork agent purchased first is placed in gas for 1.5~2.5nm high silicon MCM-41 type sieve samples
In atmosphere stove, vacuum then will be evacuated in stove for -0.09MPa, then is slowly introducing after hydrogen to normal pressure, is heated up with 5.0 DEG C/min
Speed rises to 350 DEG C, and constant temperature 10h is naturally cooling to room temperature, and hydrogen flow rate is 0.5m during this3/h。
(2) two steps in low temperature removes organic formwork agent in high silicon MCM-41 type molecular sieves
By keeping, the sample in step 1 after hydrocracking process removed template method is constant, vacuum will be evacuated in stove again, then delay
Slowly it is passed through after air to normal pressure, room temperature is naturally cooling to after constant temperature 10h again at 350 DEG C, takes out；Air stream during this
Speed is 0.5m3Hydrogen volume concentration is 90% in/h, atmosphere furnace.
(3) 0~0.1m is maintained3/ h constant air flow velocity, terminates the heating schedule of atmosphere furnace, it is naturally cooling to often
Less than 30 DEG C of temperature, is then shut off air control valve and opens the seal assembly of atmosphere furnace, finally give without organic formwork agent
Molecular screen material.
If the hydrogen volume concentration in hydrogen-holder has reached 55.0%, start batch (-type) unlatching hydrogen UF membrane and set
For the density of hydrogen come in raising system, and moderately supplement pure hydrogen gas (purity is 99.5%)；After stable, in hydrogen-holder
Gas pressure reaches 0.8MPa, and hydrogen volume concentration reaches 95.0%.The tail gas of hydrogen membrane separation plant discharge, is passed through tail gas and burns
Burn stove and carry out innoxious burning processing, the heat smoke of incinerator discharge enters flue gas heat-exchange unit, recovery waste heat by utilidor
After empty.
Embodiment 6
Same as Example 5, difference is：
Hydrogen flow rate is 0.1m3/h。
Embodiment 7
Same as Example 5, difference is：
Density of hydrogen 50%.
Comparative example 2
Conventional high-temperature calcination method removes organic formwork agent in high silicon MCM-41 type molecular sieves
By MCM-41 type molecular sieve powder samples as in Muffle furnace, 550 DEG C, constant temperature are risen to 1 DEG C/min heating rates
10h, is naturally cooling to room temperature, takes out and molecular screen material is made.
Infrared spectrum is carried out to molecular screen material made from MCM-41 types sieve sample, embodiment 5~7 and comparative example 2
Characterize, infrared table is carried out to sieve sample using the TENSOR27 FTISs of German Bruker companies
Levy, the sign condition is：Scanning range is 4000~400cm-1, resolution ratio is 4cm-1, KBr tablettings.Accompanying drawing 3A and accompanying drawing 3B are
Its testing result, as shown in figs.3 a and 3b.
As shown in figs.3 a and 3b, only molecular sieve is as former state and the sample of embodiment 6 has 2800-3000cm-1The C-H at place is strong flexible
Vibration peak and 1350-1500cm-1The C-H at place is good for flexural vibrations peak, shows to remain in the sample of embodiment 6 and stays undecomposed organic mould
Plate agent.Thus draw：Fully achieved using two steps in low temperature removing process at the effect of conventional high-temperature calcine technology, and heat
Reason temperature can drop to 350 DEG C by 550 DEG C.Its result also shows that, when density of hydrogen is higher than 50%, density of hydrogen is to template
The influence very little of agent removal effect, but influence of the hydrogen flow rate to template removal effect is significantly, hydrogen flow rate is the bigger the better.
For the high silicon MCM-15 types molecular sieve powder sample done experiment, preferably, optimum operation condition is the effect of embodiment 7：Hydrogen
Concentration 50%, hydrogen flow rate is 0.5m3/h。
The effect that heating rate and air velocity remove organic formwork agent to low temperature also has certain influence, and heating rate is lower
Better, the higher the better for air velocity.For high silicon SBA-15 types molecular sieve powder sample, its optimum operation condition is：Heating speed
Rate is 5.0 DEG C/min, and air velocity is 0.5m3/ h, density of hydrogen 50% and hydrogen flow rate are 0.5m3/h。
Embodiment 8
Referring to shown in Fig. 1 and Fig. 4：
The present invention technical process be：
Remove in high silicon porous material before organic formwork agent, first mended into low pressure hydrogen storage tank 5 enabling equipment low temperature
Pure hydrogen gas is filled, the gas pressure in low pressure hydrogen storage tank 5 is reached 0.5~1.0MPa；Temperature programmed control atmosphere furnace 1 is existed simultaneously
Sealed under normal temperature and vacuumize degassing；Carry out low temperature Template removal when, hydrogen-rich gas by hydrogen regulating valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the discharge of temperature programmed control atmosphere furnace top, passes through hydrogen
After cooler 3 and low pressure hydrogen circulating pump 4, recycled into low pressure hydrogen storage tank 5；Complete a low temperature hydrogenation cracking removing
After the operation of organic formwork agent, again temperature programmed control atmosphere furnace 1 is carried out vacuumizing degassing and open air compressor 2, then
Carry out the operation that low temperature air oxidation removes organic formwork agent again, dry air by air control valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the emptying of the top of temperature programmed control atmosphere furnace 1；Finally, close
Close the temperature control program of temperature programmed control atmosphere furnace 1 and turn air mass flow down, make after it is naturally cooling to below 30 DEG C of normal temperature, to close empty
Gas regulating valve and the seal assembly for opening atmosphere furnace, finally give clean and flawless high silicon porous material.Whole low temperature takes off
During organic formwork agent, the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0~99.0%；Work as pressure hydrogen
When hydrogen volume concentration in gas storage tank 5 is less than 60.0%, batch (-type) opens the hydrogen that hydrogen membrane separation plant 6 comes in raising system
Gas concentration, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%；When the gas pressure in low pressure hydrogen storage tank 5
Power be less than 0.5MPa when, it is necessary to supplement pure hydrogen gas (purity>99.0%), up to the gas pressure in low pressure hydrogen storage tank 5>
0.75MPa；The tail gas that hydrogen membrane separation plant 6 is discharged, is passed through tail gas burning furnace 7 and carries out innoxious burning processing, burn fire grate
The heat smoke gone out, is entered after flue gas heat-exchange unit, recovery waste heat by utilidor and emptied.
A kind of method that two steps in low temperature removes organic formwork agent, comprises the following steps：
(1) organic formwork agent in the high silicon MFI-type molecular sieve of low temperature hydrogenation cracking removing
First the aperture containing organic formwork agent purchased is placed in atmosphere furnace for 0.55nm high silicon MFI-type molecular sieve sample,
Then vacuum will be evacuated in stove for -0.09MPa, then is slowly introducing after hydrogen to normal pressure, is risen to 1.0 DEG C/min heating rates
300 DEG C, constant temperature 20h is naturally cooling to room temperature, and hydrogen flow rate is 0.5m during this3/h。
(2) two steps in low temperature removes organic formwork agent in high silicon MFI-type molecular sieve
By keeping, the sample in step 1 after hydrocracking process removed template method is constant, vacuum will be evacuated in stove again, then delay
Slowly it is passed through after air to normal pressure, room temperature is naturally cooling to after constant temperature 20h again at 300 DEG C, takes out；Air stream during this
Speed is 0.5m3/h。
(3) 0~0.1m is maintained3/ h constant air flow velocity, terminates the heating schedule of atmosphere furnace, it is naturally cooling to often
Less than 30 DEG C of temperature, is then shut off air control valve and opens the seal assembly of atmosphere furnace, finally give without organic formwork agent
Molecular screen material.
Embodiment 9
Same as Example 8, difference is：
Constant temperature 10h at 300 DEG C in step 1 and step 2.
Embodiment 10
Same as Example 8, difference is：
Constant temperature 10h at 350 DEG C in step 1 and step 2.
Comparative example 3
Conventional high-temperature calcination method removes organic formwork agent in high silicon MFI-type molecular sieve
By high silicon MFI-type molecular sieve powder sample as in Muffle furnace, 500 DEG C, constant temperature are risen to 1 DEG C/min heating rates
10h, is naturally cooling to room temperature, takes out obtained molecular screen material.
Molecular screen material is made to high silicon MFI-type molecular sieve sample, embodiment 8~10 and comparative example 3 and carries out Raman spectrum
Detection, using the LabRAM HR800-LS55 type FT-Raman and confocal Raman instrument of French Horiba Jobin Yvon companies
Levy sieve sample, a length of 325nm of incident light wave of laser, scanning range is 200cm-1~4000cm-1, its testing result
As shown in Figure 4.
As shown in figure 4, only molecular sieve is as former state and the sample of embodiment 9 has 2900-3000cm-1- the CH at place3Stretching vibration
Peak, shows to remain in the sample of embodiment 9 and stays undecomposed organic formwork agent.Thus draw：Using two steps in low temperature removing process
The effect of conventional high-temperature calcine technology is fully achieved, and heat treatment temperature can drop to 300 DEG C by 500 DEG C.Its result
Also show, also there are certain influence heat treatment temperature and time to the effect of low temperature removing organic formwork agent, and heat treatment temperature is lower
It is longer that constant temperature time needs.For high silicon MFI-type molecular sieve powder sample, effect made from embodiment 8 is best, optimum operation
Condition is：Heat treatment temperature is 300 DEG C, and constant temperature time is 20h.
Embodiment 11
Referring to shown in Fig. 1 and Fig. 5：
The present invention technical process be：
Remove in high silicon porous material before organic formwork agent, first mended into low pressure hydrogen storage tank 5 enabling equipment low temperature
Pure hydrogen gas is filled, the gas pressure in low pressure hydrogen storage tank 5 is reached 0.5~1.0MPa；Temperature programmed control atmosphere furnace 1 is existed simultaneously
Sealed under normal temperature and vacuumize degassing；Carry out low temperature Template removal when, hydrogen-rich gas by hydrogen regulating valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the discharge of temperature programmed control atmosphere furnace top, passes through hydrogen
After cooler 3 and low pressure hydrogen circulating pump 4, recycled into low pressure hydrogen storage tank 5；Complete a low temperature hydrogenation cracking removing
After the operation of organic formwork agent, again temperature programmed control atmosphere furnace 1 is carried out vacuumizing degassing and open air compressor 2, then
Carry out the operation that low temperature air oxidation removes organic formwork agent again, dry air by air control valve with constant flow rate by
The bottom of temperature programmed control atmosphere furnace 1 is passed through, through after high silicon porous material, from the emptying of the top of temperature programmed control atmosphere furnace 1；Finally, close
Close the temperature control program of temperature programmed control atmosphere furnace 1 and turn air mass flow down, make after it is naturally cooling to below 30 DEG C of normal temperature, to close empty
Gas regulating valve and the seal assembly for opening atmosphere furnace, finally give clean and flawless high silicon porous material.Whole low temperature takes off
During organic formwork agent, the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0~99.0%；Work as pressure hydrogen
When hydrogen volume concentration in gas storage tank 5 is less than 60.0%, batch (-type) opens the hydrogen that hydrogen membrane separation plant 6 comes in raising system
Gas concentration, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%；When the gas pressure in low pressure hydrogen storage tank 5
Power be less than 0.5MPa when, it is necessary to supplement pure hydrogen gas (purity>99.0%), up to the gas pressure in low pressure hydrogen storage tank 5>
0.75MPa；The tail gas that hydrogen membrane separation plant 6 is discharged, is passed through tail gas burning furnace 7 and carries out innoxious burning processing, burn fire grate
The heat smoke gone out, is entered after flue gas heat-exchange unit, recovery waste heat by utilidor and emptied.
A kind of method that two steps in low temperature removes organic formwork agent, comprises the following steps：
(1) organic formwork agent in the high silicon MFI-type molecular screen membrane of low temperature hydrogenation cracking removing
Homemade aperture containing organic formwork agent is first placed in atmosphere furnace for 0.55nm high silicon MFI-type molecular sieve membrane sample
In, vacuum then will be evacuated in stove for -0.09MPa, then be slowly introducing after hydrogen to normal pressure, with 1.0 DEG C/min heating rates
300 DEG C are risen to, constant temperature 20h is naturally cooling to room temperature, hydrogen flow rate is 0.25m during this3/h。
(2) two steps in low temperature removes organic formwork agent in high silicon MFI-type molecular screen membrane
By keeping, the sample in step 1 after hydrocracking process removed template method is constant, vacuum will be evacuated in stove again, then delay
Slowly it is passed through after air to normal pressure, room temperature is naturally cooling to after constant temperature 20h again at 300 DEG C, takes out；Air stream during this
Speed is similarly 0.25m3/h。
(3) 0~0.1m is maintained3/ h constant air flow velocity, terminates the heating schedule of atmosphere furnace, it is naturally cooling to often
Less than 30 DEG C of temperature, is then shut off air control valve and opens the seal assembly of atmosphere furnace, finally give without organic formwork agent
Molecular screen material.
Comparative example 4
Conventional high-temperature calcination method removes organic formwork agent in high silicon MFI-type molecular screen membrane
By molecular sieve powder sample as in Muffle furnace, 500 DEG C are risen to 1 DEG C/min heating rates, constant temperature 10h is natural
Room temperature is cooled to, is taken out.
Raman spectrum detection is carried out to the high silicon MFI-type molecular screen membrane in embodiment 11 and comparative example 4
Using the LabRAM HR800-LS55 type FT-Raman and confocal Ramans of French Horiba Jobin Yvon companies
Instrument levies sieve sample, a length of 325nm of incident light wave of laser, and scanning range is 200cm-1~4000cm-1, such as accompanying drawing 5
It is shown.
Drawn by accompanying drawing 5：The effect of conventional high-temperature calcine technology is fully achieved using two steps in low temperature removing process,
And heat treatment temperature can drop to 300 DEG C by 500 DEG C, its optimum operation condition is：Heat treatment temperature is 300 DEG C, during constant temperature
Between be 20h.
Gaseous jet simulation detection is carried out to the high silicon MFI-type molecular screen membrane in embodiment 11 and comparative example 4
Using the routine inspection method in document：The diaphragm prepared is put into stainless steel membrane component, film group is connected
Part gas circuit；By adjusting flow so that film front end keeps certain pressure, film rear end connects the gas of soap bubble flowmeter measuring diaphragm
Body permeation flux, or connection gas-chromatography (GC2014) investigate the gas separation effect of diaphragm；Experimentation is using gas
50%CO2/ 50%N2Hybrid standard gas.As shown in Figure 6, as a result show, use two steps in low temperature removing process completely can be with
The template effect of conventional high-temperature calcine technology is reached, and it is possible to prevente effectively from the intergranular produced by high-temperature heat treatment lacks
Fall into, be conducive to improving the membrane separating effect of MFI molecular screen membranes.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and the embodiment simultaneously is not used to limit this hair
Bright the scope of the claims, all equivalence enforcements or change without departing from carried out by the present invention are intended to be limited solely by the scope of patent protection of this case
In.
Claims (7)
1. a kind of method that two steps in low temperature removes organic formwork agent, it is characterised in that comprise the following steps：
1) first the molecular screen membrane containing organic formwork agent is positioned in atmosphere furnace, then will be vacuumized in the atmosphere furnace, slowly
It is passed through after hydrogen to normal pressure, 300~350 DEG C is risen to 1.0~10 DEG C/min heating rates, and constant temperature makes organic formwork agent abundant
Decompose；
2) after the step (1) completes, keep step 1 thermostat temperature constant, then will be vacuumized in stove, then open air and adjust
Valve is saved, is slowly introducing after dry air to normal pressure, air constant temperature oxidation processing is carried out to the high silicon porous material；
3) maintain constant air flow velocity to be more than 0 and be less than or equal to 0.1m3/ h, terminates the heating schedule of atmosphere furnace, is naturally cooling to it
Normal temperature, is then shut off air control valve and opens the seal assembly of atmosphere furnace, finally gives the high silicon without organic formwork agent many
Porous materials.
2. the method that two steps in low temperature according to claim 1 removes organic formwork agent, it is characterised in that the step 1
In high silicon porous material to have aperture be 0.3~30 nanometer of orderly pore passage structure, including silicon, oxygen and aluminium element, wherein silicon
The mol ratio of element and aluminium element is more than 50.
3. the method that two steps in low temperature according to claim 1 removes organic formwork agent, it is characterised in that the step 1
Hydrogen flow rate is 0.1~0.5m in middle 10~20h of constant temperature, thermostatic process3/h。
4. the method that two steps in low temperature according to claim 1 removes organic formwork agent, it is characterised in that the step 2
Middle 10~20h of constant temperature, air velocity is 0.1~0.5m3/h。
5. the method that two steps in low temperature according to claim 1 removes organic formwork agent, it is characterised in that the step 1
Constant temperature time with 300 DEG C of processing in step 2 is 20h, and the constant temperature time of 350 DEG C of processing is 10h.
6. the method that two steps in low temperature according to claim 1 removes organic formwork agent, it is characterised in that the step 1
Hydrogen volume concentration in middle atmosphere furnace is not less than 50.0%.
7. the method that two steps in low temperature according to claim 1 removes organic formwork agent, it is characterised in that step 1 is provided
Described in hydrogen hydrogen-holder in the gas pressure that is not less than in 60.0%, hydrogen-holder of hydrogen volume concentration be not less than
0.5MPa。
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