CN105217649A - A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method - Google Patents
A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method Download PDFInfo
- Publication number
- CN105217649A CN105217649A CN201510708752.8A CN201510708752A CN105217649A CN 105217649 A CN105217649 A CN 105217649A CN 201510708752 A CN201510708752 A CN 201510708752A CN 105217649 A CN105217649 A CN 105217649A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- temperature
- organic formwork
- formwork agent
- atmosphere furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of method that two steps in low temperature removes organic formwork agent, comprise the steps: 1) the high silicon porous material containing organic formwork agent is positioned in atmosphere furnace, vacuumize in atmosphere furnace, logical hydrogen is to normal pressure, rise to 300 ~ 350 DEG C with 1.0 ~ 10 DEG C/min temperature rise rate, constant temperature makes organic formwork agent fully decompose; 2) keep step 1 thermostat temperature constant, vacuumize in stove, open artificial atmosphere valve, pass into air to normal pressure, the process of air constant temperature oxidation is carried out to high silicon porous material; 3) 0 ~ 0.1m is maintained
3the air velocity of/h, stops the heating schedule of atmosphere furnace, and Temperature fall, to normal temperature, closes the seal assembly that atmosphere furnace opened by air control valve, obtains not containing the high silicon porous material of organic formwork agent.Present invention process mild condition, simple to operate, with low cost, suitability are wide, and the planningization being not only conducive to high silicon porous material is produced, and is 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, be specifically related to a kind of two steps in low temperature and remove the method for organic formwork agent and realize the device of the method.
Background technology
In recent years, high silicon porous material is owing to having larger specific surface area, homogeneous and on nano-scale continuously adjustable regular pore passage structure, the series of advantages such as surface group is functionalisable receive extensive concern, become the study hotspot in catalysis and parting material field.Research finds, utilize geometry and the electronics constraint characteristic in high silicon porous material duct, can reach the object of stabilized nanoscale particle shape, structure and electronic property, can be the catalyzer constructing low temperature high activity provides carrier-mediated catalyzer to provide carrier.High-silica zeolite particle in high silicon porous material can also be cross-linked with each other and be grown to serve as fine and close high-silica zeolite film; it has regular pore passage structure, good chemical stability, physical strength, thermostability and catalytic performance; in the field such as membrane separation technique and membrane catalytic reaction, there is potential using value, also result in the extensive concern of investigators.
Mostly need when preparing synthesizing high-silicon porous material to add organic formwork agent, to form the porous material with special pore passage structure; Need again before use to remove organic formwork agent by high-temperature calcination technique, to make duct result unimpeded.But, due to the difference of thermal expansion direction and amplitude between porous material self different orientation, and the difference of hot expansion property between porous material and prop carrier, make high silicon porous material at high temperature form skeleton because of thermal stresses to subside and the intergranular defect such as crackle, these defects significantly can reduce its catalytic separation characteristic.Thus, the intergranular defect formed when thermal treatment removes organic formwork agent how is effectively avoided to become the severe challenge restricting high silicon porous material preparation and application technical development.Result of study finds, time below the calcining temperature to 350 DEG C reducing template, is conducive to the regular pore passage structure keeping high silicon porous material.
In recent years, the research that low temperature removed organic formwork agent in high silicon porous material has become the hot issue of many focus of attentions.The method that existing low temperature removes organic formwork agent mainly comprises two classes: a kind of is template by using strong oxidizer oxidation removal height silicon porous material, and its oxidant species comprises ozone, hydrogen peroxide and potassium permanganate etc.; Another kind carrys out removed template method by physico-chemical process, adopts the technology such as solvent extraction, microwave, overcritical and cold plasma to remove the agent of high silicon porous material inner formword.But these two class methods are more is for high silicon mesoporous material, as SBA-15 and MCM-41 etc.; And for the more high silicon poromerics of application, but because template and cell walls bonding force are handed over by force, and cause it to be still difficult to effective elimination organic formwork agent at low temperatures.In addition, these existing low temperature removed template method techniques above-mentioned generally all need special plant and instrument, its operating procedure is also comparatively complicated, therefore urgently develops the technology and equipment that a kind of high efficient cryogenic being applicable to different pore size height silicon porous material removes organic formwork agent.
Summary of the invention
One object of the present invention is to provide a kind of two steps in low temperature to remove the method for organic formwork agent, it adopts the method for low temperature hydrogenation cracking and air constant temperature oxidation to remove organic formwork agent, the method overcomes low temperature in existing high silicon porous material preparation technology and removes the technical bottleneck of organic formwork agent, there is provided a kind of processing condition gentle, the template low temperature removing process that process is simple and with low cost.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
Two steps in low temperature removes a method for organic formwork agent, it is characterized in that, comprises the steps:
1) first the high silicon porous material containing organic formwork agent is positioned in atmosphere furnace, then vacuumize in described atmosphere furnace, after slowly passing into hydrogen to normal pressure, rise to 300 ~ 350 DEG C with 1.0 ~ 10 DEG C/min temperature rise rate, and constant temperature makes organic formwork agent fully decompose;
2), after described step (1) completes, keep step 1 thermostat temperature constant, then vacuumize in stove, then open artificial atmosphere valve, after slowly passing into dry air to normal pressure, the process of air constant temperature oxidation is carried out to described high silicon porous material;
3) 0 ~ 0.1m is maintained
3the constant air flow velocity of/h, stops the heating schedule of atmosphere furnace, makes its Temperature fall to normal temperature, then closes air control valve and opens the seal assembly of atmosphere furnace, finally obtaining not containing the high silicon porous material of organic formwork agent.
Low temperature hydrogenation cracking technique and low temperature air oxidation technology creatively organically combine by the present invention, and the efficient cryogenic preferably resolving organic formwork agent in high silicon porous material removes a difficult problem.Low temperature hydrogenation cracking technology is adopted to make the most of organic formwork agent in porous material resolve into small organic molecule, thus cell channels is opened, adopt Cryogenic air calcining process to make remaining lacking in porous material stay organic formwork agent and air fully to contact also complete oxidation, finally realize removing completely of organic formwork agent in porous material.
Preferably, the high silicon porous material in described step 1 has the orderly pore passage structure that aperture is 0.3 ~ 30 nanometer, and comprise silicon, oxygen and aluminium element, wherein the mol ratio of element silicon and aluminium element is greater than 50.
Preferably, described high silicon porous material is sieve particle or molecular screen membrane.High-silica zeolite porous material has multiple, the minimum high silicon MFI-type molecular sieve of the high silicon MCM-41 type molecular sieve that the SBA-15 type molecular sieve selecting aperture maximum in the present invention, aperture are placed in the middle and aperture.
Preferably, constant temperature 10 ~ 20h in described step 1, in thermostatic process, hydrogen flow rate is 0.1 ~ 0.5m
3/ h.
Preferably, constant temperature 10 ~ 20h in described step 2, air velocity is 0.1 ~ 0.5m
3/ h.
Preferably, in described step 1 and step 2, the constant temperature times of 300 DEG C of process are 20h, and the constant temperature times of 350 DEG C of process are 10h.
Preferably, the hydrogen volume concentration in described step 1 in atmosphere furnace is not less than 50.0%.
Preferably, provide the hydrogen volume concentration in the hydrogen-holder of hydrogen described in step 1 to be not less than 60.0%, the gaseous tension in hydrogen-holder is not less than 0.5MPa.
Another object of the present invention is that providing a kind of realizes the device that two steps in low temperature removes the method for organic formwork agent, and this device is simple, is easy to large-scale production.
The invention provides and a kind ofly realize the device that two steps in low temperature removes the method for organic formwork agent, the air compressor, hydrogen cooler and the low pressure hydrogen storage tank that comprise atmosphere furnace, be connected by pipeline with described atmosphere furnace, described hydrogen cooler is connected with low pressure hydrogen recycle pump, and described low pressure hydrogen storage tank is connected with hydrogen membrane separating device.
Preferably, also comprise tail gas burning furnace, described tail gas burning furnace is connected with described hydrogen membrane separating device.
Technological process of the present invention is:
Remove in high silicon porous material before organic formwork agent at the equipment low temperature of enabling, first in hydrogen-holder, supplement pure hydrogen gas, make the gaseous tension in hydrogen-holder reach 0.5 ~ 1.0MPa; Atmosphere furnace is sealed at normal temperatures and vacuumize degassing simultaneously; When carrying out low temperature Template removal, hydrogen-rich gas is passed into by atmosphere furnace bottom with constant flow rate by hydrogen regulating valve, after high silicon porous material, discharges, after hydrogen cooler, enter hydrogen-holder and recycle from atmosphere furnace top; Complete after a low temperature hydrogenation cracking removes the operation of organic formwork agent, again vacuumize degassing carried out to atmosphere furnace and open air compressor, and then carry out the operation that a time low temperature air oxidation removes organic formwork agent, dry air is passed into by atmosphere furnace bottom with constant flow rate by air control valve, after high silicon porous material, emptying from atmosphere furnace top; Finally, close the temperature control program of atmosphere furnace and turn air flow quantity down, after making its Temperature fall to normal temperature less than 30 DEG C, close air control valve and open the seal assembly of atmosphere furnace, finally obtaining cleaning and flawless high silicon porous material.Whole low temperature removes in organic formwork agent process, and the hydrogen volume concentration in atmosphere furnace maintains 50.0 ~ 99.0%; When the hydrogen volume concentration in hydrogen-holder lower than 60.0% time, intermittent type opens the density of hydrogen that hydrogen membrane separating device comes in raising system, until the hydrogen volume concentration in hydrogen-holder reaches 90.0%; When the gaseous tension in hydrogen-holder is lower than 0.5MPa, need supplementary pure hydrogen gas (purity >99.0%), until the gaseous tension >0.75MPa in hydrogen-holder; The tail gas that hydrogen membrane separating device is discharged, passes into tail gas burning furnace and carries out innoxious burn processing, and the heat smoke that incinerator is discharged enters flue gas heat-exchange unit by utilidor, emptying after recovery waste heat.
The invention has the beneficial effects as follows:
(1) adopt low temperature hydrogenation cracking technology to make the most of organic formwork agent in porous material resolve into small organic molecule, thus cell channels is opened;
(2) adopt low temperature air oxidation calcining process to make remaining lacking in porous material stay organic formwork agent and air fully to contact also complete oxidation, finally realize removing completely of organic formwork agent in porous material;
(3) present invention process mild condition, operation is more simple, cost is more cheap, suitability is wider, the planningization being not only conducive to high silicon porous material is produced, and is conducive to the industrialization of porous, inorganic membrane separation technique.
Accompanying drawing explanation
Accompanying drawing 1 removes organic formwork agent process flow sheet for two steps in low temperature of the present invention;
Accompanying drawing 2 is the thermogravimetric curve figure removing high silicon SBA-15 type sieve particle under the different temperature rise rate of the embodiment of the present invention 1 ~ 4 and air velocity, wherein (a) is the molecular sieve former state containing organic formwork agent, and (b) is 0.1m for temperature rise rate is 10 DEG C/min and air velocity
3sample after/h removed template method, (c) is 0.5m for temperature rise rate is 10 DEG C/min and air velocity
3sample after/h removed template method, (d) is 0.1m for temperature rise rate is 5.0 DEG C/min and air velocity
3sample after/h removed template method, (e) is 0.5m for temperature rise rate is 5.0 DEG C/min and air velocity
3sample after/h removed template method, (f) is the sample after 500 DEG C of conventional high-temperature calcining removed template methods;
Accompanying drawing 3A and 3B is the infrared spectrum removing high silicon MCM-41 type molecular screen membrane under the embodiment of the present invention 5 ~ 7 different hydrogen concentration and hydrogen flow rate, wherein (a) is the molecular sieve former state containing organic formwork agent, (b) for density of hydrogen 90% and hydrogen flow rate be 0.5m
3sample after/h removed template method, (c) for density of hydrogen 90% and hydrogen flow rate be 0.1m
3sample after/h removed template method, (d) for density of hydrogen 50% and hydrogen flow rate be 0.5m
3sample after/h removed template method, (e) is the sample after 500 DEG C of conventional high-temperature calcining removed template methods;
Accompanying drawing 4 is the Raman spectrograms removing high silicon MFI-type molecular sieve particle under the embodiment of the present invention 8 ~ 10 differing temps and constant temperature time, wherein (a) is the molecular sieve former state containing organic formwork agent, b () is the sample at 300 DEG C after constant temperature 20h removed template method, c () is the sample at 300 DEG C after constant temperature 10h removed template method, d () is the sample at 350 DEG C after constant temperature 10h removed template method, (e) is the sample after 500 DEG C of conventional high-temperature calcining removed template methods;
Accompanying drawing 5 is the Raman spectrograms removing high silicon MFI-type molecular sieve film under the embodiment of the present invention 11 different operating condition, wherein diaphragm M
3-1for low temperature hydrogenation cracking result, wherein diaphragm M
3-2for low temperature air oxidation result, wherein diaphragm M
3-3for conventional high-temperature results for calcination;
Accompanying drawing 6 is the CO removing high silicon MFI-type molecular sieve film under the embodiment of the present invention 11 different operating condition
2/ N
2separating effect, wherein diaphragm M
3-1for low temperature hydrogenation cracking result, wherein diaphragm M
3-2for low temperature air oxidation result, wherein diaphragm M
3-3for conventional high-temperature results for calcination;
Description of reference numerals: 1, temperature programming atmosphere furnace, 2, air compressor, 3, hydrogen cooler, 4, low pressure hydrogen recycle pump, 5, low pressure hydrogen storage tank, 6, hydrogen membrane separating device, 7, tail gas burning furnace.
Embodiment
Below in conjunction with specific examples, illustrate the present invention further.Should be appreciated that, these embodiments only for illustration of the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of technician and adjustment, still belong to protection scope of the present invention in actual applications.
Except special instruction, the equipment that the present invention uses and reagent are the conventional commercial products of the art, and the method that the present invention adopts is the method that the art routine uses.Normal temperature and pressure is in the present invention: temperature is 25 degree, and normal pressure is 0.1MPa.In Fig. 1, the direction of arrow is the flow direction of gas.
High-silica zeolite porous material has multiple, the minimum high silicon MFI-type molecular sieve of the high silicon MCM-41 type molecular sieve that the SBA-15 type molecular sieve selecting aperture maximum in the present invention, aperture are placed in the middle and aperture.Wherein SBA-15 type molecular sieve, high silicon MCM-41 type molecular sieve and high silicon MFI-type molecular sieve are purchased from catalysis factory of Nankai University.
Adopt the TENSOR27 Fourier transform infrared spectrometer of German Bruker company to carry out infrared detection, adopt the LabRAMHR800-LS55 type FT-Raman and confocal Raman instrument of French HoribaJobinYvon company to carry out Raman spectrum detection.
Embodiment 1
Shown in Fig. 1 and Fig. 2:
Technological process of the present invention is:
Remove in high silicon porous material before organic formwork agent at the equipment low temperature of enabling, first in low pressure hydrogen storage tank 5, supplement pure hydrogen gas, make the gaseous tension in low pressure hydrogen storage tank 5 reach 0.5 ~ 1.0MPa; Temperature programmed control atmosphere furnace 1 is sealed at normal temperatures and vacuumize degassing simultaneously; When carrying out low temperature Template removal, hydrogen-rich gas is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by hydrogen regulating valve, after high silicon porous material, discharge from temperature programmed control atmosphere furnace top, after hydrogen cooler 3 and low pressure hydrogen recycle pump 4, enter low pressure hydrogen storage tank 5 and recycle; Complete after a low temperature hydrogenation cracking removes the operation of organic formwork agent, again vacuumize degassing carried out to temperature programmed control atmosphere furnace 1 and open air compressor 2, and then carry out the operation that a time low temperature air oxidation removes organic formwork agent, dry air is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by air control valve, after high silicon porous material, emptying from temperature programmed control atmosphere furnace 1 top; Finally, the temperature control program of bolt down procedure temperature control atmosphere furnace 1 also turns air flow quantity down, after making its Temperature fall to normal temperature less than 30 DEG C, closes air control valve and opens the seal assembly of atmosphere furnace, finally obtains clean and flawless high silicon porous material.Whole low temperature removes in organic formwork agent process, and the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0 ~ 99.0%; When the hydrogen volume concentration in low pressure hydrogen storage tank 5 lower than 60.0% time, intermittent type opens the density of hydrogen that hydrogen membrane separating device 6 comes in raising system, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%; When the gaseous tension in low pressure hydrogen storage tank 5 is lower than 0.5MPa, need supplementary pure hydrogen gas (purity >99.0%), until the gaseous tension >0.75MPa in low pressure hydrogen storage tank 5; The tail gas that hydrogen membrane separating device 6 is discharged, passes into tail gas burning furnace 7 and carries out innoxious burn processing, and the heat smoke that incinerator is discharged enters flue gas heat-exchange unit by utilidor, emptying after recovery waste heat.
Two steps in low temperature removes a method for organic formwork agent, comprises the following steps:
(1) low temperature hydrogenation cracking removes organic formwork agent in high silicon SBA-15 type molecular sieve
Be first that the high silicon SBA-15 type sieve sample of 15 ~ 30nm is placed in temperature programmed control atmosphere furnace by what purchase containing organic formwork agent aperture, then vacuum tightness will be evacuated in atmosphere furnace for-0.09MPa, after slowly passing into hydrogen to normal pressure again, 300 DEG C are risen to 10 DEG C/min temperature rise rate, constant temperature 20h, Temperature fall is to room temperature, and in this process, hydrogen flow rate is 0.1m
3/ h.
(2) two steps in low temperature removes organic formwork agent in high silicon SBA-15 type molecular sieve
By constant for the sample kept in step 1 after hydrocracking process removed template method, be again evacuated to vacuum by temperature programmed control atmosphere furnace, then after slowly passing into air to normal pressure, at 300 DEG C again after constant temperature 20h, Temperature fall, to room temperature, takes out; This process air flow speed is 0.1m
3/ h.
(3) 0 ~ 0.1m is maintained
3the constant air flow velocity of/h, stops the heating schedule of atmosphere furnace, makes its Temperature fall to normal temperature less than 30 DEG C, then closes air control valve and opens the seal assembly of atmosphere furnace, finally obtaining not containing the molecular screen material of organic formwork agent.
Atmosphere furnace service routine temperature control atmosphere furnace in the present embodiment, but atmosphere furnace of the present invention is not limited to a service routine temperature control atmosphere furnace, and other have the atmosphere furnace of identical function all within protection scope of the present invention.In the present embodiment step 1, be evacuated to-0.09MPa by atmosphere furnace, the pressure range that the present invention vacuumizes is not limited to-0.09MPa, and the pressure range that those skilled in the art can expect is all within protection scope of the present invention.
Embodiment 2
Identical with embodiment 1, difference is:
Air velocity is 0.5m
3/ h.
Embodiment 3
Identical with embodiment 1, difference is:
Temperature rise rate is 5.0 DEG C/min.
Embodiment 4
Identical with embodiment 2, difference is:
Temperature rise rate is 5.0 DEG C/min, and air velocity is 0.5m
3/ h.
Comparative example 1
Conventional high-temperature calcination method removes organic formwork agent in high silicon SBA-15 type molecular sieve
By molecular sieve powder sample as in retort furnace, rise to 500 DEG C, constant temperature 10h with 1 DEG C/min temperature rise rate, Temperature fall, to room temperature, takes out obtained molecular screen material.
The molecular screen material obtained to high silicon SBA-15 type sieve sample, embodiment 1 ~ 4 and comparative example 1 carries out thermogravimetric detection respectively:
Adopt the STA409C Thermal Synthetic Analysis instrument of German Netzsch company to enter thermogravimetric to sieve sample to characterize, this operation of equipment condition is: air is carrier gas, and with the ramp to 800 DEG C of 20 DEG C/min, accompanying drawing 2 is its detected result.
Can be drawn by Fig. 2, adopt two steps in low temperature removing process can reach the effect of conventional high-temperature calcining process completely, but thermal treatment temp can drop to 300 DEG C by 500 DEG C, its result shows, temperature rise rate and air velocity also have certain influence to the effect that low temperature removes organic formwork agent, temperature rise rate is more low better, and air velocity is more high better.For tested high silicon SBA-15 type molecular sieve powder sample, the effect of embodiment 4 is best, and therefore optimum operation condition is: temperature rise rate is 5.0 DEG C/min and air velocity is 0.5m
3/ h.
Embodiment 5
Shown in Fig. 1, Fig. 3 A and Fig. 3 B:
Technological process of the present invention is:
Remove in high silicon porous material before organic formwork agent at the equipment low temperature of enabling, first in low pressure hydrogen storage tank 5, supplement pure hydrogen gas, make the gaseous tension in low pressure hydrogen storage tank 5 reach 0.5 ~ 1.0MPa; Temperature programmed control atmosphere furnace 1 is sealed at normal temperatures and vacuumize degassing simultaneously; When carrying out low temperature Template removal, hydrogen-rich gas is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by hydrogen regulating valve, after high silicon porous material, discharge from temperature programmed control atmosphere furnace top, after hydrogen cooler 3 and low pressure hydrogen recycle pump 4, enter low pressure hydrogen storage tank 5 and recycle; Complete after a low temperature hydrogenation cracking removes the operation of organic formwork agent, again vacuumize degassing carried out to temperature programmed control atmosphere furnace 1 and open air compressor 2, and then carry out the operation that a time low temperature air oxidation removes organic formwork agent, dry air is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by air control valve, after high silicon porous material, emptying from temperature programmed control atmosphere furnace 1 top; Finally, the temperature control program of bolt down procedure temperature control atmosphere furnace 1 also turns air flow quantity down, after making its Temperature fall to normal temperature less than 30 DEG C, closes air control valve and opens the seal assembly of atmosphere furnace, finally obtains clean and flawless high silicon porous material.Whole low temperature removes in organic formwork agent process, and the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0 ~ 99.0%; When the hydrogen volume concentration in low pressure hydrogen storage tank 5 lower than 60.0% time, intermittent type opens the density of hydrogen that hydrogen membrane separating device 6 comes in raising system, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%; When the gaseous tension in low pressure hydrogen storage tank 5 is lower than 0.5MPa, need supplementary pure hydrogen gas (purity >99.0%), until the gaseous tension >0.75MPa in low pressure hydrogen storage tank 5; The tail gas that hydrogen membrane separating device 6 is discharged, passes into tail gas burning furnace 7 and carries out innoxious burn processing, and the heat smoke that incinerator is discharged enters flue gas heat-exchange unit by utilidor, emptying after recovery waste heat.
Two steps in low temperature removes a method for organic formwork agent, comprises the following steps:
(1) low temperature hydrogenation cracking removes organic formwork agent in high silicon MCM-41 type molecular sieve
Be first that the high silicon MCM-41 type sieve sample of 1.5 ~ 2.5nm is placed in atmosphere furnace by what purchase containing organic formwork agent aperture, then vacuum tightness will be evacuated in stove for-0.09MPa, after slowly passing into hydrogen to normal pressure again, 350 DEG C are risen to 5.0 DEG C/min temperature rise rate, constant temperature 10h, Temperature fall is to room temperature, and in this process, hydrogen flow rate is 0.5m
3/ h.
(2) two steps in low temperature removes organic formwork agent in high silicon MCM-41 type molecular sieve
By constant for the sample kept in step 1 after hydrocracking process removed template method, be again evacuated to vacuum by stove, then after slowly passing into air to normal pressure, at 350 DEG C again after constant temperature 10h, Temperature fall, to room temperature, takes out; This process air flow speed is 0.5m
3/ h, in atmosphere furnace, hydrogen volume concentration is 90%.
(3) 0 ~ 0.1m is maintained
3the constant air flow velocity of/h, stops the heating schedule of atmosphere furnace, makes its Temperature fall to normal temperature less than 30 DEG C, then closes air control valve and opens the seal assembly of atmosphere furnace, finally obtaining not containing the molecular screen material of organic formwork agent.
If the hydrogen volume concentration in hydrogen-holder reaches 55.0%, startup intermittent type unlatching hydrogen membrane separating device carrys out the density of hydrogen in raising system, and appropriateness supplements pure hydrogen gas (purity is 99.5%); After stable, the gaseous tension in hydrogen-holder reaches 0.8MPa, and hydrogen volume concentration reaches 95.0%.The tail gas that hydrogen membrane separating device is discharged, passes into tail gas burning furnace and carries out innoxious burn processing, and the heat smoke that incinerator is discharged enters flue gas heat-exchange unit by utilidor, emptying after recovery waste heat.
Embodiment 6
Identical with embodiment 5, difference is:
Hydrogen flow rate is 0.1m
3/ h.
Embodiment 7
Identical with embodiment 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 sieve
By MCM-41 type molecular sieve powder sample as in retort furnace, rise to 550 DEG C, constant temperature 10h with 1 DEG C/min temperature rise rate, Temperature fall, to room temperature, takes out obtained molecular screen material.
The molecular screen material obtained to MCM-41 type sieve sample, embodiment 5 ~ 7 and comparative example 2 carries out infrared spectrum characterization, adopt the TENSOR27 Fourier transform infrared spectrometer of German Bruker company to carry out Infrared Characterization to sieve sample, this sign condition is: sweep limit is 4000 ~ 400cm
-1, resolving power is 4cm
-1, KBr compressing tablet.Accompanying drawing 3A and accompanying drawing 3B is its detected result, as shown in figs.3 a and 3b.
As shown in figs.3 a and 3b, only there is 2800-3000cm in molecular sieve former state and embodiment 6 sample
-1the C-H at place is good for stretching vibration peak and 1350-1500cm
-1the C-H at place is good for flexural vibration peak, shows to remain in embodiment 6 sample to stay undecomposed organic formwork agent.Draw thus: adopt two steps in low temperature removing process can reach the effect of conventional high-temperature calcining process completely, and thermal treatment temp can drop to 350 DEG C by 550 DEG C.Its result also shows, when density of hydrogen higher than 50% time, density of hydrogen is very little on the impact of template removal effect, but hydrogen flow rate is remarkable on the impact of template removal effect, and hydrogen flow rate is the bigger the better.For the high silicon MCM-15 type molecular sieve powder sample of doing experiment, the effect of embodiment 7 is best, and optimum operation condition is: density of hydrogen 50%, and hydrogen flow rate is 0.5m
3/ h.
Temperature rise rate and air velocity also have certain influence to the effect that low temperature removes organic formwork agent, and temperature rise rate is more low better, and air velocity is more high better.For high silicon SBA-15 type molecular sieve powder sample, its optimum operation condition is: temperature rise rate is 5.0 DEG C/min, and air velocity is 0.5m
3/ h, density of hydrogen 50% and hydrogen flow rate are 0.5m
3/ h.
Embodiment 8
Shown in Fig. 1 and Fig. 4:
Technological process of the present invention is:
Remove in high silicon porous material before organic formwork agent at the equipment low temperature of enabling, first in low pressure hydrogen storage tank 5, supplement pure hydrogen gas, make the gaseous tension in low pressure hydrogen storage tank 5 reach 0.5 ~ 1.0MPa; Temperature programmed control atmosphere furnace 1 is sealed at normal temperatures and vacuumize degassing simultaneously; When carrying out low temperature Template removal, hydrogen-rich gas is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by hydrogen regulating valve, after high silicon porous material, discharge from temperature programmed control atmosphere furnace top, after hydrogen cooler 3 and low pressure hydrogen recycle pump 4, enter low pressure hydrogen storage tank 5 and recycle; Complete after a low temperature hydrogenation cracking removes the operation of organic formwork agent, again vacuumize degassing carried out to temperature programmed control atmosphere furnace 1 and open air compressor 2, and then carry out the operation that a time low temperature air oxidation removes organic formwork agent, dry air is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by air control valve, after high silicon porous material, emptying from temperature programmed control atmosphere furnace 1 top; Finally, the temperature control program of bolt down procedure temperature control atmosphere furnace 1 also turns air flow quantity down, after making its Temperature fall to normal temperature less than 30 DEG C, closes air control valve and opens the seal assembly of atmosphere furnace, finally obtains clean and flawless high silicon porous material.Whole low temperature removes in organic formwork agent process, and the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0 ~ 99.0%; When the hydrogen volume concentration in low pressure hydrogen storage tank 5 lower than 60.0% time, intermittent type opens the density of hydrogen that hydrogen membrane separating device 6 comes in raising system, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%; When the gaseous tension in low pressure hydrogen storage tank 5 is lower than 0.5MPa, need supplementary pure hydrogen gas (purity >99.0%), until the gaseous tension >0.75MPa in low pressure hydrogen storage tank 5; The tail gas that hydrogen membrane separating device 6 is discharged, passes into tail gas burning furnace 7 and carries out innoxious burn processing, and the heat smoke that incinerator is discharged enters flue gas heat-exchange unit by utilidor, emptying after recovery waste heat.
Two steps in low temperature removes a method for organic formwork agent, comprises the following steps:
(1) low temperature hydrogenation cracking removes organic formwork agent in high silicon MFI-type molecular sieve
Be first that the high silicon MFI-type molecular sieve sample of 0.55nm is placed in atmosphere furnace by what purchase containing organic formwork agent aperture, then vacuum tightness will be evacuated in stove for-0.09MPa, after slowly passing into hydrogen to normal pressure again, 300 DEG C are risen to 1.0 DEG C/min temperature rise rate, constant temperature 20h, Temperature fall is to room temperature, and in this process, hydrogen flow rate is 0.5m
3/ h.
(2) two steps in low temperature removes organic formwork agent in high silicon MFI-type molecular sieve
By constant for the sample kept in step 1 after hydrocracking process removed template method, be again evacuated to vacuum by stove, then after slowly passing into air to normal pressure, at 300 DEG C again after constant temperature 20h, Temperature fall, to room temperature, takes out; This process air flow speed is 0.5m
3/ h.
(3) 0 ~ 0.1m is maintained
3the constant air flow velocity of/h, stops the heating schedule of atmosphere furnace, makes its Temperature fall to normal temperature less than 30 DEG C, then closes air control valve and opens the seal assembly of atmosphere furnace, finally obtaining not containing the molecular screen material of organic formwork agent.
Embodiment 9
Identical with embodiment 8, difference is:
Constant temperature 10h at 300 DEG C in step 1 and step 2.
Embodiment 10
Identical with embodiment 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 powdered sample as in retort furnace, rise to 500 DEG C, constant temperature 10h with 1 DEG C/min temperature rise rate, Temperature fall, to room temperature, takes out obtained molecular screen material.
Molecular screen material is obtained to high silicon MFI-type molecular sieve sample, embodiment 8 ~ 10 and comparative example 3 and carries out Raman spectrum detection, the LabRAMHR800-LS55 type FT-Raman and confocal Raman instrument of French HoribaJobinYvon company is adopted to levy sieve sample, the lambda1-wavelength of laser apparatus is 325nm, and sweep limit is 200cm
-1~ 4000cm
-1, its detected result as shown in Figure 4.
As shown in Figure 4, only there is 2900-3000cm in molecular sieve former state and embodiment 9 sample
-1-the CH at place
3stretching vibration peak, shows to remain in embodiment 9 sample to stay undecomposed organic formwork agent.Draw thus: adopt two steps in low temperature removing process can reach the effect of conventional high-temperature calcining process completely, and thermal treatment temp can drop to 300 DEG C by 500 DEG C.Its result also shows, also there are certain influence thermal treatment temp and time to the effect that low temperature removes organic formwork agent, and it is longer that the lower constant temperature time of thermal treatment temp needs.For high silicon MFI-type molecular sieve powdered sample, the effect that embodiment 8 obtains is best, and optimum operation condition is: thermal treatment temp is 300 DEG C, and constant temperature time is 20h.
Embodiment 11
Shown in Fig. 1 and Fig. 5:
Technological process of the present invention is:
Remove in high silicon porous material before organic formwork agent at the equipment low temperature of enabling, first in low pressure hydrogen storage tank 5, supplement pure hydrogen gas, make the gaseous tension in low pressure hydrogen storage tank 5 reach 0.5 ~ 1.0MPa; Temperature programmed control atmosphere furnace 1 is sealed at normal temperatures and vacuumize degassing simultaneously; When carrying out low temperature Template removal, hydrogen-rich gas is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by hydrogen regulating valve, after high silicon porous material, discharge from temperature programmed control atmosphere furnace top, after hydrogen cooler 3 and low pressure hydrogen recycle pump 4, enter low pressure hydrogen storage tank 5 and recycle; Complete after a low temperature hydrogenation cracking removes the operation of organic formwork agent, again vacuumize degassing carried out to temperature programmed control atmosphere furnace 1 and open air compressor 2, and then carry out the operation that a time low temperature air oxidation removes organic formwork agent, dry air is passed into by temperature programmed control atmosphere furnace 1 bottom with constant flow rate by air control valve, after high silicon porous material, emptying from temperature programmed control atmosphere furnace 1 top; Finally, the temperature control program of bolt down procedure temperature control atmosphere furnace 1 also turns air flow quantity down, after making its Temperature fall to normal temperature less than 30 DEG C, closes air control valve and opens the seal assembly of atmosphere furnace, finally obtains clean and flawless high silicon porous material.Whole low temperature removes in organic formwork agent process, and the hydrogen volume concentration in temperature programmed control atmosphere furnace maintains 50.0 ~ 99.0%; When the hydrogen volume concentration in low pressure hydrogen storage tank 5 lower than 60.0% time, intermittent type opens the density of hydrogen that hydrogen membrane separating device 6 comes in raising system, until the hydrogen volume concentration in low pressure hydrogen storage tank 5 reaches 90.0%; When the gaseous tension in low pressure hydrogen storage tank 5 is lower than 0.5MPa, need supplementary pure hydrogen gas (purity >99.0%), until the gaseous tension >0.75MPa in low pressure hydrogen storage tank 5; The tail gas that hydrogen membrane separating device 6 is discharged, passes into tail gas burning furnace 7 and carries out innoxious burn processing, and the heat smoke that incinerator is discharged enters flue gas heat-exchange unit by utilidor, emptying after recovery waste heat.
Two steps in low temperature removes a method for organic formwork agent, comprises the following steps:
(1) low temperature hydrogenation cracking removes organic formwork agent in high silicon MFI-type molecular sieve film
First by homemade be that the high silicon MFI-type molecular sieve membrane sample of 0.55nm is placed in atmosphere furnace containing organic formwork agent aperture, then vacuum tightness will be evacuated in stove for-0.09MPa, after slowly passing into hydrogen to normal pressure again, 300 DEG C are risen to 1.0 DEG C/min temperature rise rate, constant temperature 20h, Temperature fall is to room temperature, and in this process, hydrogen flow rate is 0.25m
3/ h.
(2) two steps in low temperature removes organic formwork agent in high silicon MFI-type molecular sieve film
By constant for the sample kept in step 1 after hydrocracking process removed template method, be again evacuated to vacuum by stove, then after slowly passing into air to normal pressure, at 300 DEG C again after constant temperature 20h, Temperature fall, to room temperature, takes out; This process air flow speed is similarly 0.25m
3/ h.
(3) 0 ~ 0.1m is maintained
3the constant air flow velocity of/h, stops the heating schedule of atmosphere furnace, makes its Temperature fall to normal temperature less than 30 DEG C, then closes air control valve and opens the seal assembly of atmosphere furnace, finally obtaining not containing the molecular screen material of organic formwork agent.
Comparative example 4
Conventional high-temperature calcination method removes organic formwork agent in high silicon MFI-type molecular sieve film
By molecular sieve powder sample as in retort furnace, rise to 500 DEG C, constant temperature 10h with 1 DEG C/min temperature rise rate, Temperature fall, to room temperature, takes out.
Raman spectrum detection is carried out to the high silicon MFI-type molecular sieve film in embodiment 11 and comparative example 4
Adopt the LabRAMHR800-LS55 type FT-Raman and confocal Raman instrument of French HoribaJobinYvon company to levy sieve sample, the lambda1-wavelength of laser apparatus is 325nm, and sweep limit is 200cm
-1~ 4000cm
-1, as shown in Figure 5.
Drawn by accompanying drawing 5: adopt two steps in low temperature removing process can reach the effect of conventional high-temperature calcining process completely, and thermal treatment temp can drop to 300 DEG C by 500 DEG C, its optimum operation condition is: thermal treatment temp is 300 DEG C, and constant temperature time is 20h.
Gaseous jet simulation detection is carried out to the high silicon MFI-type molecular sieve film in embodiment 11 and comparative example 4
Adopt the routine inspection method in document: the diaphragm prepared is put into stainless steel membrane assembly, connects membrane module gas circuit; By the pressure that adjust flux makes film front end keep certain, film rear end connects the gas-permeable flux of soap bubble flowmeter measuring diaphragm, or connects the gas separation effect that gas-chromatography (GC2014) investigates diaphragm; Experimentation uses gas to be 50%CO
2/ 50%N
2hybrid standard gas.As shown in Figure 6, result shows, adopt two steps in low temperature removing process can reach the template effect of conventional high-temperature calcining process completely, and effectively can avoid the intergranular defect that produces because of high-temperature heat treatment, be conducive to the membrane separating effect improving MFI molecular screen membrane.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and this embodiment is also not used to limit the scope of the claims of the present invention, and the equivalence that all the present invention of disengaging do is implemented or changed, and all should be contained in the scope of patent protection of this case.
Claims (10)
1. two steps in low temperature removes a method for organic formwork agent, it is characterized in that, comprises the steps:
1) first the high silicon porous material containing organic formwork agent is positioned in atmosphere furnace, then vacuumize in described atmosphere furnace, after slowly passing into hydrogen to normal pressure, rise to 300 ~ 350 DEG C with 1.0 ~ 10 DEG C/min temperature rise rate, and constant temperature makes organic formwork agent fully decompose;
2), after described step (1) completes, keep step 1 thermostat temperature constant, then vacuumize in stove, then open artificial atmosphere valve, after slowly passing into dry air to normal pressure, the process of air constant temperature oxidation is carried out to described high silicon porous material;
3) 0 ~ 0.1m is maintained
3the constant air flow velocity of/h, stops the heating schedule of atmosphere furnace, makes its Temperature fall to normal temperature, then closes air control valve and opens the seal assembly of atmosphere furnace, finally obtaining not containing the high silicon porous material of organic formwork agent.
2. two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, high silicon porous material in described step 1 has the orderly pore passage structure that aperture is 0.3 ~ 30 nanometer, and comprise silicon, oxygen and aluminium element, wherein the mol ratio of element silicon and aluminium element is greater than 50.
3. two steps in low temperature according to claim 1 and 2 removes the method for organic formwork agent, it is characterized in that, described high silicon porous material is sieve particle or molecular screen membrane.
4. two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, constant temperature 10 ~ 20h in described step 1, and in thermostatic process, hydrogen flow rate is 0.1 ~ 0.5m
3/ h.
5. two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, constant temperature 10 ~ 20h in described step 2, and air velocity is 0.1 ~ 0.5m
3/ h.
6. two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, in described step 1 and step 2, the constant temperature times of 300 DEG C of process are 20h, and the constant temperature times of 350 DEG C of process are 10h.
7. two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, the hydrogen volume concentration in described step 1 in atmosphere furnace is not less than 50.0%.
8. two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, provide the hydrogen volume concentration in the hydrogen-holder of hydrogen described in step 1 to be not less than 60.0%, the gaseous tension in hydrogen-holder is not less than 0.5MPa.
9. one kind realizes the device that two steps in low temperature according to claim 1 removes the method for organic formwork agent, it is characterized in that, the air compressor, hydrogen cooler and the low pressure hydrogen storage tank that comprise atmosphere furnace, be connected by pipeline with described atmosphere furnace, described hydrogen cooler is connected with low pressure hydrogen recycle pump, and described low pressure hydrogen storage tank is connected with hydrogen membrane separating device.
10. according to claim 9ly realize the device that two steps in low temperature removes the method for organic formwork agent, it is characterized in that, also comprise tail gas burning furnace, described tail gas burning furnace is connected with described hydrogen membrane separating device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510708752.8A CN105217649B (en) | 2015-10-26 | 2015-10-26 | A kind of method of two steps in low temperature removing organic formwork agent and the device for realizing this method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510708752.8A CN105217649B (en) | 2015-10-26 | 2015-10-26 | A kind of method of two steps in low temperature removing organic formwork agent and the device for realizing this method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105217649A true CN105217649A (en) | 2016-01-06 |
| CN105217649B CN105217649B (en) | 2017-10-27 |
Family
ID=54987005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510708752.8A Active CN105217649B (en) | 2015-10-26 | 2015-10-26 | A kind of method of two steps in low temperature removing organic formwork agent and the device for realizing this method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105217649B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109465021A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MFI type structure molecular sieve as the isomerization catalyst preparation method of carrier |
| CN111151147A (en) * | 2020-02-12 | 2020-05-15 | 泰州九润环保科技有限公司 | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173434A (en) * | 2010-12-30 | 2011-09-07 | 天津凯美思特科技发展有限公司 | Method for removing template in industrial production process of MCM-41 molecular sieves |
| CN103351005A (en) * | 2013-06-18 | 2013-10-16 | 宁夏大学 | Method for rapidly removing organic template from cellular material |
-
2015
- 2015-10-26 CN CN201510708752.8A patent/CN105217649B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173434A (en) * | 2010-12-30 | 2011-09-07 | 天津凯美思特科技发展有限公司 | Method for removing template in industrial production process of MCM-41 molecular sieves |
| CN103351005A (en) * | 2013-06-18 | 2013-10-16 | 宁夏大学 | Method for rapidly removing organic template from cellular material |
Non-Patent Citations (1)
| Title |
|---|
| 赵淑蘅等: "低温加氢裂解脱除高硅ZSM-5分子筛内TPAOH模板剂", 《物理化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109465021A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院大连化学物理研究所 | It is a kind of using MFI type structure molecular sieve as the isomerization catalyst preparation method of carrier |
| CN109465021B (en) * | 2017-09-07 | 2021-10-08 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst with MFI-structure molecular sieve as carrier |
| CN111151147A (en) * | 2020-02-12 | 2020-05-15 | 泰州九润环保科技有限公司 | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105217649B (en) | 2017-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sadiq et al. | A pilot‐scale demonstration of mobile direct air capture using metal‐organic frameworks | |
| CN107824210A (en) | A kind of titanium dioxide composite photocatalyst of N doping mesoporous carbon parcel and its preparation method and application | |
| CN101822931B (en) | Decompression regeneration system and method for hollow fiber membrane contactor of carbon dioxide enriched absorbent solution | |
| CN104198223A (en) | Online particle sampling unit of minitype fluidized bed and application thereof | |
| CN203507783U (en) | Skid-mounted carbon dioxide membrane separation device | |
| CN105217649A (en) | A kind of two steps in low temperature removes the method for organic formwork agent and realizes the device of the method | |
| CN203961935U (en) | CO in carbon dioxide drive producing well output gas-liquid 2recycle device | |
| EP2623195A1 (en) | Photocatalytic gas conversion device | |
| CN108948368B (en) | Method for rapidly preparing nickel-based metal organic framework material | |
| Campbell et al. | Continuous flow solar desorption of CO2 from aqueous amines | |
| CN101773767A (en) | Internal circulation closed type CO2 film photocatalytic reduction reaction device and reduction method thereof | |
| CN212532869U (en) | Integrated fixed bed reactor for co-pyrolysis of biomass and waste plastic | |
| CN104388105A (en) | Device and method for producing synthetic gas by continuous two-stage catalytic pyrolysis | |
| Masud et al. | Methane refinement by iron oxide, packed column water scrubbing, and activated charcoal scrubbing techniques | |
| CN207430071U (en) | A kind of emission-control equipment for reducing PVC floor production line VOC emission amount | |
| CN107088401B (en) | Rapid CO production using ionic liquid additives2Method for producing adsorbent | |
| Kwan et al. | Energy and exergetic analysis of applying solar cascade utilization to an artificial photosynthesis energy supply system | |
| CN109529908A (en) | A kind of porous g-C3N4The preparation method and applications of material | |
| CN114768479A (en) | Eutectic solvent for efficiently absorbing carbon dioxide gas and preparation method and application thereof | |
| CN209537409U (en) | Biogas film purifies integrating device | |
| Haiyu et al. | Simulation, experimentation and analyzation of vacuum pressure swing adsorption process for CO2 capture from dry flue gas | |
| CN113365724A (en) | Reactor cascade and method for operating a reactor cascade | |
| CN220633667U (en) | Carbon dioxide entrapment auxiliary device | |
| CN106744710B (en) | Method for producing sodium hydrosulfide by continuous process | |
| CN104549189A (en) | Porous TiO2 film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |