CN114904357B - Method for adsorbing styrene - Google Patents
Method for adsorbing styrene Download PDFInfo
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- CN114904357B CN114904357B CN202110184798.XA CN202110184798A CN114904357B CN 114904357 B CN114904357 B CN 114904357B CN 202110184798 A CN202110184798 A CN 202110184798A CN 114904357 B CN114904357 B CN 114904357B
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- membered ring
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 239000003463 adsorbent Substances 0.000 claims abstract description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 13
- 239000005046 Chlorosilane Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 10
- 239000012855 volatile organic compound Substances 0.000 abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
- B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for adsorbing styrene, which adopts an adsorbent to adsorb styrene; the adsorbent is a twelve-membered ring molecular sieve; the silicon-aluminum ratio of the twelve-membered ring molecular sieve is as follows: siO (SiO) 2 /Al 2 O 3 =500 to 1000; specific surface area=600 to 850m 2 And/g. The twelve-membered ring molecular sieve provided by the invention can be used for adsorbing macromolecular volatile organic compounds, and particularly has adsorption performance far superior to that of a common adsorption material under the condition of high ambient humidity.
Description
Technical Field
The invention belongs to the technical field of inorganic synthesis; relates to a method for adsorbing styrene.
Background
The emission of Volatile Organic Compounds (VOCs) is a serious hazard to natural environment and human health, and an adsorption method and a catalytic oxidation method are effective methods for treating the VOCs. The kinetic diameter of the VOCs molecules is generally smaller than 1nm, and when the pore diameter of the adsorbent is matched with the kinetic diameter of the VOCs molecules, the adsorbed organic molecules are not easy to escape. The common microporous adsorption material mainly comprises active carbon and zeolite molecular sieve, wherein the active carbon has larger specific surface area and better performance, but has poorer thermal stability, is easy to burn, has more difficult desorption of VOCs molecules and faces the problem of dangerous waste treatment. The zeolite is a microporous crystalline material, has higher specific surface area and microporous pore volume, and also has regular pore channels and cages. Meanwhile, zeolite also has very high thermal stability and hydrothermal stability, and has been widely used in the field of VOCs adsorption.
The MFI molecular sieve adsorbent has wide application, has larger adsorption capacity to VOCs molecules such as acetone, butanone, benzene, toluene and the like, and has adjustable SiO 2 /Al 2 O 3 Even under the condition of high molecular environment humidity, the adsorption performance of the ZSM-5 adsorbent is not changed greatly, so that the ZSM-5 adsorbent can be used for adsorbing and purifying organic pollutants under the condition of high humidity. However, for VOCs molecules (such as styrene, etc.) with critical diameters larger than the aperture of ZSM-5 molecular sieve, the molecules cannot enter micropores of the molecular sieve, so that the performance of the molecules is extremely poor in the adsorption process of macromolecular VOCs such as styrene, etc. The ten-binary-ring microporous molecular sieve has larger pore size and very good adsorption performance on large-size VOCs molecules such as styrene, but usually the SiO of the ten-binary-ring microporous molecular sieve 2 /Al 2 O 3 The adsorption of organic compound molecules is affected by low-adsorption water, the static water absorption is more than 25 percent, and H is used for 2 O molecules and VOCs molecules are competitively adsorbed in zeolite pore channels, so that the adsorption performance of the zeolite pore channels is greatly reduced under the condition of higher ambient humidity, the adsorption capacity is reduced by more than 20 times, and the zeolite pore channels cannot be used in the adsorption process under the condition of higher ambient humidity.
Disclosure of Invention
The application discloses a method for adsorbing styrene, which adopts an adsorbent to adsorb styrene; the adsorbent is a twelve-membered ring molecular sieve; the molecular sieve can be used for adsorbing macromolecular volatile organic compounds, in particular to the adsorption process of macromolecular VOCs under larger environmental humidity.
According to one aspect of the present application, a method is disclosedA method for adsorbing styrene, wherein an adsorbent is used for adsorbing styrene; the adsorbent is a twelve-membered ring molecular sieve; the silicon-aluminum ratio of the twelve-membered ring molecular sieve is as follows: siO (SiO) 2 /Al 2 O 3 =500 to 1000; specific surface area=600 to 850m 2 /g。
Optionally, the twelve-membered ring molecular sieve has a silicon to aluminum ratio of: siO (SiO) 2 /Al 2 O 3 ＝500～850。
Optionally, the specific surface area of the twelve-membered ring molecular sieve is 600-750 m 2 /g。
Optionally, the adsorption is dynamic adsorption; the dynamic adsorption includes: and (3) contacting the mixed gas containing the styrene with an adsorbent for adsorption, so that the styrene can be adsorbed.
Optionally, the mixture gas containing styrene further comprises at least one of steam, nitrogen, air and oxygen.
Preferably, the dynamic adsorption comprises: the nitrogen carries saturated steam and steam of styrene respectively to be adsorbed by the adsorbent bed layer, so that the styrene can be adsorbed.
Optionally, the volume space velocity of the mixture gas containing the styrene is 10000-15000 h -1 。
Preferably, the volume space velocity of the mixed gas is 12000h -1 。
Optionally, the temperature of the adsorption is 20-60 ℃.
Preferably, the temperature of the adsorption is 40 ℃.
Optionally, the concentration of the styrene in the mixture gas containing the styrene is 200-500 mg/m 3 。
Preferably, the concentration of the styrene in the mixture gas containing styrene is 300mg/m 3 。
Optionally, the twelve-membered ring molecular sieve is FAU or BEA type twelve-membered ring molecular sieve; the FAU or BEA type twelve-membered ring molecular sieve has the following silicon-aluminum ratio: siO (SiO) 2 /Al 2 O 3 ＝550～850。
Optionally, the FAU or BEA twelve-membered ring molecular sieve is SiO 2 /Al 2 O 3 The upper limit is selected from 600, 650, 700, 750, 800, or 850; the lower limit is selected from 550, 600, 650, 700, 750, or 800.
Preferably, the twelve-membered ring molecular sieve is a FAU or BEA type twelve-membered ring molecular sieve; the FAU or BEA type twelve-membered ring molecular sieve has the following silicon-aluminum ratio: siO (SiO) 2 /Al 2 O 3 =550 to 850; the static water absorption of 1g of the FAU or BEA type twelve-membered ring molecular sieve is not higher than 30mg.
Optionally, the method for preparing the twelve-membered ring molecular sieve at least comprises the following steps: chlorosilane treatment, water washing, acid washing and roasting.
Preferably, the method comprises: (1) Mixing chlorosilane-containing material with at least one of NaY molecular sieve and Beta molecular sieve, and reacting to obtain an intermediate product I; (2) Washing the intermediate product I with water to obtain an intermediate product II; (3) Acid washing is carried out on the intermediate product II to obtain an intermediate product III; (4) Roasting the intermediate product III to obtain the twelve-membered ring molecular sieve.
Optionally, in the step (1), the reaction conditions are: the temperature is 400-550 ℃ and the time is 10-240 min.
Optionally, the SiCl 4 The upper limit of the treatment temperature is 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃ or 550 ℃, and the lower limit of the treatment temperature is 400 ℃, 420 ℃, 440 ℃, 450 ℃, 460 ℃, 480 ℃ or 520 ℃.
Optionally, the SiCl 4 The upper limit of the treatment time is selected from 30min, 60min, 90min, 120min, 180min or 240min, and the lower limit is selected from 10min, 30min, 60min, 90min, 120min or 180min.
Optionally, the chlorosilane is N 2 Or air-borne chlorosilane saturated steam or heated chlorosilane conveyed by a pump.
Optionally, the N 2 Or the air flow is 10-120 ml/min.
Optionally, the N 2 Or air flow rate is selected from 20ml/min, 30ml/min, 40ml/min, 50ml/min, 60ml/min, 70ml/min, 80ml/min, 90ml/min, or 100ml/min, and lower limit is selected from 10ml/L, 20ml/min, 30ml/min, 40ml/min, 50ml/min, 60ml/min, 70ml/min, 80ml/min or 90ml/min.
Optionally, the flow rate of the heated chlorosilane conveyed by the pump is 0.1-0.3 ml/min.
Optionally, the pump delivers heated chlorosilane at an upper flow limit selected from 0.15ml/min, 0.2ml/min, 0.25ml/min, or 0.3ml/min; the lower limit is selected from 0.1ml/min, 0.15ml/min, 0.2ml/min or 0.25ml/min.
Optionally, the step (1) includes: mixing chlorosilane-containing material with at least one of NaY molecular sieve and Beta molecular sieve, and reacting to obtain an intermediate product I.
Optionally, in the step (2), the conditions of the water washing are: the solid ratio of the water washing liquid is 2-50 cm 3 And/g, the water washing time is 1-24 h.
Optionally, the upper limit of the solid ratio of the water washing liquid is selected from 5cm 3 /g、10cm 3 /g、15cm 3 /g、20cm 3 /g、25cm 3 /g、30cm 3 /g、40cm 3 /g or 50cm 3 The lower limit of the ratio is 2cm 3 /g、5cm 3 /g、10cm 3 /g、15cm 3 /g、20cm 3 /g、25cm 3 /g、30cm 3 /g or 40cm 3 /g。
Optionally, the upper limit of the water washing time is selected from 4h, 6h, 8h, 12h, 16h, 20h or 24h, and the lower limit is selected from 1h, 4h, 6h, 8h, 12h, 16h or 20h.
Alternatively, the water wash is washing intermediate I to near neutrality with deionized water.
Optionally, in the step (3), the conditions of the pickling are: the temperature is 60-100 ℃, the acid concentration is 0.1-3.0 mol/L, and the liquid-solid ratio is 2-30 cm 3 And/g, the time is 2-12 h.
Optionally, the upper limit of the pickling temperature is selected from 70 ℃, 80 ℃, 90 ℃ or 100 ℃, and the lower limit of the pickling temperature is selected from 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
Optionally, the upper limit of the pickling concentration is selected from 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L or 3.0mol/L, and the lower limit of the pickling concentration is selected from 0.1mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L or 2.5mol/L.
Optionally, the upper limit of the solid ratio of the water washing liquid is selected from 5cm 3 /g、10cm 3 /g、15cm 3 /g、20cm 3 /g、25cm 3 /g or 30cm 3 The lower limit of the ratio is 2cm 3 /g、5cm 3 /g、10cm 3 /g、15cm 3 /g、20cm 3 /g or 25cm 3 /g。
Optionally, the upper limit of the pickling time is selected from 4h, 6h, 8h, 10h or 12h, and the lower limit is selected from 2h, 4h, 6h, 8h or 10h.
Optionally, the acid used is at least one selected from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, and citric acid.
Optionally, after the step (3), the method further includes: washed to near neutrality with deionized water.
Optionally, in the step (4), the roasting condition is: the two-stage temperature programming mode is adopted; the temperature rising condition of the first section is as follows: the temperature is 200-350 ℃, and the heating rate is less than or equal to 5 ℃/min; the temperature rising condition of the first section is as follows: the temperature is 350-650 ℃, the temperature rising rate is less than or equal to 10 ℃/min, and the time is 1-8h.
Optionally, the upper temperature limit of the first temperature increasing section is selected from 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃; the lower limit is selected from 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃ and 340 ℃. The upper limit heating rate is selected from 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min.
Optionally, the upper temperature limit of the second temperature raising section is selected from 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 650 ℃; the lower limit is selected from 350 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃ and 620 ℃. The upper limit heating rate is selected from 2 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min or 10 ℃/min.
Optionally, the upper limit of the roasting time is selected from 2h, 3h, 4h, 5h, 6h, 7h and 8h; the lower limit is selected from 1h, 2h, 3h, 4h, 5h, 6h and 7h.
The temperature programming roasting is continuous roasting for 1-8h when the temperature is raised to the highest temperature.
Optionally, before said step (4), further comprising drying said intermediate III; the drying conditions are as follows: the temperature is 80-200 ℃ and the time is 3-12 h.
Alternatively, the amount of styrene adsorbed by 1g of the twelve-membered ring molecular sieve is 100 to 200mg.
Alternatively, when the weight of the water vapor is more than 50% by weight of the mixture gas containing styrene (i.e., when the humidity is more than 50%), the dynamic adsorption styrene amount of 1g of the twelve-membered ring molecular sieve is 100 to 200mg.
Alternatively, 1g of the twelve-membered ring molecular sieve has a static water absorption of less than 30mg.
Preferably, 1g of the twelve-membered ring molecular sieve has a static water absorption of less than 28mg.
Alternatively, the upper limit of the static water uptake (GB/T6287-1986) of 1g of the twelve-membered ring molecular sieve is selected from 2, 8, 12, 18, 20, 22, 23, 24, 25, 26, 27 or 28mg; the lower limit is selected from 1, 2, 8, 12, 18, 20, 22, 23, 24, 25, 26 or 27mg.
Wherein the water absorption amount refers to the mass of the adsorbent when the adsorbent adsorbs water/does not adsorb water; the styrene adsorption amount is the mass of styrene adsorbed by the adsorbent/the mass of the adsorbent when not adsorbed.
Specifically, the 3.0% means that 1g of water that the adsorbent can adsorb has a mass of 30 mg; the 10% means that 1g of the adsorbent can adsorb styrene with a mass of 100 mg.
The excellent effects produced by the present application include:
the application provides a method for adsorbing styrene, and the twelve-membered ring molecular sieve provided by the application has a complete micropore structure, and has BET specific surface area of 600-850 m 2 /g，SiO 2 /Al 2 O 3 500-1000 g of the twelve-membered ringThe static water absorption of the sub-sieve is lower than 30mg (compared with the static water absorption of 1g of the traditional ten-binary-ring zeolite is higher than 200 mg), and the dynamic styrene is adsorbed to 100-200 mg (the environmental humidity is higher than 50%), so that the material can be used in the adsorption process of the macromolecular VOCs under the higher environmental humidity, and shows excellent hydrophobicity and the adsorption performance of the macromolecular VOCs, which is far superior to other adsorption materials.
The preparation method of the twelve-membered ring molecular sieve provided by the application adopts a isomorphous replacement-water washing-acid washing-drying-roasting series treatment process, greatly improves the selectivity and the hydrophobicity of the twelve-membered ring molecular sieve, has the characteristics of simple operation, low-cost and easily-obtained raw materials, good repeatability and the like, and is easy for industrial large-scale production.
Drawings
FIG. 1 is a schematic diagram of a dynamic adsorption device for styrene according to an embodiment of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially. The analytical methods in this application, unless otherwise specified, all employ conventional analytical methods and conventional instrumentation.
The static water absorption method is measured by the method of GB/T6287-1986.
The styrene adsorption amount is obtained by a dynamic adsorption test method, and the specific operation is as follows: the nitrogen carries the saturated steam and the steam of the styrene to be adsorbed by the adsorption bed layer, and the concentration of the styrene in the gas after passing through the adsorbent bed layer is analyzed by on-line chromatography.
The specific surface area is Micromeritics ASAP-2020N 2 The silicon-aluminum ratio is measured by an adsorption instrument and is measured by a Zetium model X-ray fluorescence spectrometer, and the online chromatographic analyzer is derived from Tianmei GC7980.
The solid ratio of the washing liquid in the examples refers to the volume of water and the mass ratio of the treated sample; the liquid-solid ratio of the acid washing refers to the mass ratio of the volume of hydrochloric acid to the solid obtained in the previous step.
The water absorption refers to the mass of the adsorbent as adsorbed/unadsorbed water; the styrene adsorption amount is the mass of styrene adsorbed by the adsorbent/the mass of the adsorbent when not adsorbed.
Example 1
Using N 2 Carrying chlorosilane saturated steam and 20 g NaY solid at 500 ℃ for 60min, N 2 The flow rate is 120ml/min; washing the treated sample with water for 12h at a water-wash solution solid ratio of 30cm 3 Washing with deionized water to neutrality and stoving; treating with 0.5mol/L hydrochloric acid at 100deg.C for 4 hr to obtain a liquid-solid ratio of 20cm 3 Washing with deionized water to be nearly neutral, and baking at 127 ℃ for 12 hours; and finally, heating the dried sample to 350 ℃ at a heating rate of 5 ℃/min, heating to 600 ℃ at a heating rate of 10 ℃/min, and roasting for 4 hours at 600 ℃.
Through detection, the obtained sample SiO 2 /Al 2 O 3 650, a specific surface area of 710m 2 /g。
Example 2
The chlorosilane conveyed by a pump is heated and treated with 20 g of NaY solid for 90min at 450 ℃ with the flow of 0.15ml/min; washing the treated sample with water for 6 hr at a water-wash solution solid ratio of 5cm 3 Washing with deionized water to neutrality and stoving; treating with 2.0mol/L hydrochloric acid at 80deg.C for 6 hr to obtain a liquid-solid ratio of 10cm 3 Washing with deionized water to be nearly neutral, and baking at 130 ℃ for 12 hours; and finally, heating the dried sample to 320 ℃ at a heating rate of 3 ℃/min, heating to 500 ℃ at a heating rate of 8 ℃/min, and roasting for 4 hours at 500 ℃.
Through detection, the obtained sample SiO 2 /Al 2 O 3 550, a specific surface area of 690m 2 /g。
Example 3
Treating with air-borne chlorosilane saturated steam and 20 g Beta molecular sieve solid at 550deg.C for 30min, N 2 The flow rate is 90ml/min; washing the treated sample with water for 12h at a water-wash solution solid ratio of 30cm 3 Washing with deionized water to neutrality and stoving; treating with 1.0mol/L hydrochloric acid at 100deg.C for 6 hr to obtain a liquid-solid ratio of 15cm 3 Washing with deionized water to be nearly neutral, and baking at 110 ℃ for 12 hours; finally, the dried sample is treated with 2 ℃ for +.The temperature rising rate in min is increased to 300 ℃, then the temperature rising rate in 6 ℃/min is increased to 600 ℃, and the roasting is carried out for 4 hours at 600 ℃.
Through detection, the obtained sample SiO 2 /Al 2 O 3 800, specific surface area 650m 2 /g。
Example 4
Process of adsorbing styrene:
as shown in fig. 1, three gases such as nitrogen, saturated steam of styrene carried by nitrogen, saturated steam carried by nitrogen and the like are uniformly mixed by a mixer, then pass through an adsorbent bed (the gas flow is accurately controlled by a mass flowmeter), the tail gas is adsorbed by on-line chromatographic analysis, and the rest of the tail gas is discharged by a gas washing bottle. The humidity of the VOCs gas is analyzed by adopting a hygrometer, the temperature of an adsorption bed layer is controlled by a heating furnace, and the volume airspeed, the concentration of the VOCs and the temperature of a humidity uniform mass flowmeter and a generator are controlled.
The static adsorption amount was measured according to GB/T6287-1986.
TABLE 1 static Water absorption and dynamic styrene adsorption for catalysts under different reaction conditions
Because the silicon aluminum of the traditional low-silicon Beta and Y zeolite is relatively low, in the styrene adsorption process with the environmental humidity of 50%, the adsorption quantity of the styrene is lower than 50mg due to the competition adsorption of water and the styrene in the process. The high-silicon Y and high-silicon Beta zeolite in the invention have better hydrophobicity, and the static water absorption is lower than 30mg, so that the high-silicon Y and high-silicon Beta zeolite show higher adsorption capacity in the styrene adsorption process.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (13)
1. A method for adsorbing styrene is characterized in that,
adsorbing styrene by using an adsorbent; the adsorbent is a twelve-membered ring molecular sieve; the silicon-aluminum ratio of the twelve-membered ring molecular sieve is as follows: siO (SiO) 2 /Al 2 O 3 =500 to 800; specific surface area=600 to 710m 2 /g；
The twelve-membered ring molecular sieve is FAU or BEA type twelve-membered ring molecular sieve;
the method for preparing the twelve-membered ring molecular sieve comprises the following steps:
a. mixing chlorosilane-containing material with at least one of NaY molecular sieve and Beta molecular sieve, and reacting to obtain an intermediate product I;
b. washing the intermediate product I with water to obtain an intermediate product II;
c. acid washing is carried out on the intermediate product II to obtain an intermediate product III;
d. roasting the intermediate product III to obtain the twelve-membered ring molecular sieve;
in the step d, the roasting conditions are as follows: the two-stage temperature programming mode is adopted;
the temperature rising condition of the first section is as follows: the temperature is 200-350 ℃, and the heating rate is less than or equal to 5 ℃/min;
the temperature rising condition of the first section is as follows: the temperature is 350-650 ℃, the temperature rising rate is less than or equal to 10 ℃/min, and the time is 1-8h.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the adsorption is dynamic adsorption; the dynamic adsorption includes: and (3) contacting the mixed gas containing the styrene with an adsorbent for adsorption, so that the styrene can be adsorbed.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the mixed gas containing the styrene also comprises at least one of water vapor, nitrogen, air and oxygen.
4. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the volume airspeed of the mixture gas containing the styrene is 10000-15000 h -1 。
5. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the adsorption temperature is 20-60 ℃.
6. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the concentration of the styrene in the mixture gas containing the styrene is 200-500 mg/m 3 。
7. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the FAU or BEA type twelve-membered ring molecular sieve has the following silicon-aluminum ratio: siO (SiO) 2 /Al 2 O 3 =550~800。
8. The method of claim 1, wherein the step of determining the position of the substrate comprises,
in the step a, the reaction conditions are as follows: the temperature is 400-550 ℃ and the time is 10-240 min.
9. The method of claim 1, wherein the step of determining the position of the substrate comprises,
in the step b, the conditions of the water washing are as follows: the solid ratio of the water washing liquid is 2-50 cm 3 And/g, the water washing time is 1-24 h.
10. The method of claim 1, wherein the step of determining the position of the substrate comprises,
in the step c, the conditions of the acid washing are as follows: the temperature is 60-100 ℃, the acid concentration is 0.1-3.0 mol/L, the liquid-solid ratio is 2-30 cm < 3 >/g, and the time is 2-12 h.
11. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the amount of styrene adsorbed by 1g of the twelve-membered ring molecular sieve is 100-200 mg.
12. The method of claim 3, wherein the step of,
when the weight of the water vapor is more than 50% of the weight of the mixture gas containing the styrene, the dynamic adsorption styrene amount of 1g of the twelve-membered ring molecular sieve is 100-200 mg.
13. The method of claim 3, wherein the step of,
the static water absorption of 1g of the twelve-membered ring molecular sieve is less than 30mg.
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