CN106902734A - It is a kind of that there is adsorbent of good storage perfume and sustained release performance and preparation method thereof to geranyl acetone - Google Patents
It is a kind of that there is adsorbent of good storage perfume and sustained release performance and preparation method thereof to geranyl acetone Download PDFInfo
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- CN106902734A CN106902734A CN201710105012.4A CN201710105012A CN106902734A CN 106902734 A CN106902734 A CN 106902734A CN 201710105012 A CN201710105012 A CN 201710105012A CN 106902734 A CN106902734 A CN 106902734A
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- molecular sieve
- adsorbent
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- water
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 44
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 title claims abstract description 38
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000003860 storage Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000013268 sustained release Methods 0.000 title claims abstract description 18
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 18
- 239000002304 perfume Substances 0.000 title claims abstract description 8
- 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 67
- 239000002808 molecular sieve Substances 0.000 claims abstract description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 28
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims abstract description 27
- 239000008101 lactose Substances 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 235000013599 spices Nutrition 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 241000921313 Phyllopodium Species 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 12
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 20
- 238000003795 desorption Methods 0.000 description 14
- 239000003205 fragrance Substances 0.000 description 13
- 238000010792 warming Methods 0.000 description 10
- 235000019504 cigarettes Nutrition 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0003—Compounds of unspecified constitution defined by the chemical reaction for their preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Fats And Perfumes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
There is adsorbent of good storage perfume and sustained release performance and preparation method thereof to geranyl acetone the invention discloses a kind of.The method is comprised the following steps：First lactose is mixed at normal temperatures with water, carbodiimide solution is obtained.Again by molecular sieve addition carbodiimide solution, after stirring mixing, mixture is filtered and dried, obtain the molecular sieve that saturation has adsorbed carburization agent.Then the molecular sieve that saturation has adsorbed carburization agent is put into tube furnace, is carbonized under a nitrogen, carbonization molecular sieve is obtained after cooling.The molecular sieve that will be carbonized again is added in tube furnace, is heated up under nitrogen atmosphere, then gas is switched into hydrogen, is carried out surface reduction and is modified, and obtains modified molecular screen.Finally modified molecular screen is soaked with watery hydrochloric acid, then with distillation washing, dry adsorbent.Modified molecular screen of the invention has more acid adsorption site；By controllable surface chemical modification, the strong adsorption group in part in adsorbent surface is converted into weakly stable group, weakens its adsorption to geranyl acetone.
Description
Technical field
The invention belongs to technical field of cigarettes, more particularly to a kind of have good storage fragrant to geranyl acetone and sustained release performance
Adsorbent and preparation method thereof.
Background technology
Geranyl acetone there is fresh fragrance of a flower fragrance, slightly sweet charm, therefore geranyl acetone to pass through and has frequently as one kind
[Yang Hongming, Yang Qianxu, Chen Jianming, et al. are a kind of prominent during the spices for having the fresh and sweet note that can strengthen flue gas is added into cigarette
Show the essence and its application [P] .2014 in cigarette of fresh and sweet fragrant style and features].Applying to the sustained release essence of cigarette
Material to essence, it is necessary to have outside preferably desorption release performance, in addition it is also necessary to have certain storage perfume ability so that in cigarette-opening
Essence and flavoring agent is not allowed volatile after bag, and former after cigarette-opening bag little with last several sensory difference.And existing cigarette
With adsorbent it is difficult to have both both.
According to [a kind of ozone method of modifying of cigarette activated carbons of Chen Senli, Kong Haohui, Chen Meili, et al. and application [P]
.2014] report, the method being modified using ozone produces a kind of cigarette activated carbon, mainly by improving the surface acid of activated carbon
Property radical amount strengthen the adsorption of activated carbon and spices, so as to reach improve spices retention rate on the activated carbon
Purpose, but by modified, desorption rate is not improved.And [a kind of cigarette filter adsorbent [P] .1995 of the full of Liu Li]
Indefiniteness aluminosilicate adsorbent is prepared as the fragrant material of storage, after finding to volatilize 30 days in atmosphere, the retention rate of spices can be with
80% is reached, but the adsorbent only considered the adhesion of enhancing spices and adsorbent, be not involved with releasing for fragrance material
Put problem.
This project main inventive is a kind of have good storage fragrant to geranyl acetone and sustained release performance adsorbent preparation
Method, for solving contradiction and deficiency on fragrant for the storage of geranyl acetone spices in the prior art and sustained release performance, prepares
Go out a kind of fragrant slow-release material of geranyl acetone storage, it not only has the storage energy for keeping or improving adsorbent to adsorb geranyl acetone
Power, meanwhile, its release performance to geranyl acetone, the potentiality with practical application can be improved again.
The content of the invention
Have good storage fragrant to geranyl acetone and adsorbent and its preparation side of sustained release performance the invention provides a kind of
Method, for solving in the prior art, the problem that release performance and storage fragrance can have both very well after addition spices in cigarette.
The present invention is realized by following concrete technical scheme.
The inventive method includes the preparation of carbodiimide solution：Lactose is mixed at normal temperatures with water, lactose is dissolved in water
In.The preparation of the molecular sieve of saturation absorption carburization agent：Molecular sieve is added in carbodiimide solution, by stirring mixing certain hour
Afterwards, after mixture filter and dry at high temperature, the molecular sieve that saturation has adsorbed carburization agent is obtained.Surface carbonation：Will
The molecular sieve that saturation has adsorbed carburization agent is put into tube furnace, and high temperature cabonization is carried out under the atmosphere of nitrogen, is obtained after cooling
Carbonization molecular sieve.Surface reduction is modified：Carbonization molecular sieve is added in tube furnace, is heated up under nitrogen atmosphere, then by gas
Hydrogen is switched to, surface reduction is carried out at high temperature and is modified.Separate out impurity：Modified molecular screen is soaked with a certain amount of watery hydrochloric acid,
Again with distilled water after, be dried to obtain required sample.
A kind of preparation method to adsorbent of the geranyl acetone with good storage perfume and sustained release performance, including following step
Suddenly：
(1) lactose is mixed with water, is dissolved in water lactose, produced and obtain carbodiimide solution；
(2) molecular sieve is added in carbodiimide solution, after stirring mixing, after mixture is filtered and dried, is satisfied
With the molecular sieve for having adsorbed carburization agent；
(3) molecular sieve that saturation in step (2) has adsorbed carburization agent is put into tube furnace, enters under the atmosphere of nitrogen
Row carbonization, obtains carbonization molecular sieve after cooling；
(4) carbonization molecular sieve is added in tube furnace, after first heating up under nitrogen atmosphere, then gas is switched into hydrogen
Gas, carries out surface reduction and is modified, and is then cooled to room temperature；
(5) with the modified molecular screen obtained by watery hydrochloric acid soaking step (4), then cleaned with water, finally dried i.e. available
Have good storage fragrant to geranyl acetone and sustained release performance adsorbent.
Preferably, step (1) lactose and the mixed proportion of water are 1-7g lactose：100mL water.
Preferably, step (1) mixing is carried out at normal temperatures.
Preferably, the molecular sieve described in step (2) and the mixing ratio of carbodiimide solution are 1-5g molecular sieves:100mL carbodiimide solutions.
Preferably, the temperature of carbonization is 200 DEG C -400 DEG C in step (3).
Preferably, the time of carbonization is 0.5-6h in step (3).
Preferably, the surface reduction modified time is 1h-5h in step (4).
Preferably, the modified temperature of surface reduction is 100 DEG C -300 DEG C in step (4), and heating rate is 2 DEG C/min-10
℃/min。
Preferably, the concentration of watery hydrochloric acid is 0.01-1mol/L in step (5), and meets modified molecular sieve and watery hydrochloric acid
Solid-to-liquid ratio be 1-5g solids：10mL hydrochloric acid.
Preferably, the time of immersion is 5min-20min in step (5).
Preferably, a kind of preparation method to adsorbent of the geranyl acetone with good storage perfume and sustained release performance, including
Following steps：
(1) by lactose and water with 1-7g lactose：The ratio of 100mL water mixes at normal temperatures, is dissolved in water lactose, system
Obtain carbodiimide solution；
(2) by molecular sieve and carbodiimide solution with 1-5g molecular sieves:The ratio of 100mL carbodiimide solutions is mixed, and fills molecular sieve
Lactose in point absorption carbodiimide solution, then, filter and it is dry at high temperature after, obtain the molecular sieve that saturation has adsorbed carburization agent；
(3) molecular sieve in step (2) is put into tube furnace, 200 DEG C -400 DEG C is warming up under the atmosphere of nitrogen,
0.5h-6h is kept, carbonization molecular sieve is obtained after cooling；
(4) the carbonization molecular sieve in step (3) is added in tube furnace, 100 DEG C -300 is warming up under nitrogen atmosphere
After DEG C, hydrogen stream is passed through, continues 1h-5h, be then cooled to room temperature；
(5) 0.01mol/L-1mol/L watery hydrochloric acid is used again, is 1-5g solids by solid-to-liquid ratio：The ratio of 10mL hydrochloric acid, immersion
Through after the molecular sieve mixture that hydrogen reducing is processed, being cleaned with distilled water, finally drying can be obtained to be had to geranyl acetone
The adsorbent of good storage perfume and sustained release performance.
Compared with prior art, the invention has the advantages that：
Adsorbent prepared by the present invention, on the one hand with more acid adsorption site, can improve or keep material to perfume (or spice)
The adsorption capacity of phyllopodium acetone；On the other hand, by controllable surface chemical modification, the part in adsorbent surface is adsorbed by force
Group is converted into weakly stable group, has weakened its adsorption to geranyl acetone.The long and is：It is modified,
Absorption bit quantity does not change, and adsorption has weakened, so as to realize effectively discharging fragrant on the premise of adsorbance is constant
The performance of phyllopodium acetone.
Brief description of the drawings
Fig. 1 is the TPD curve maps on geranyl acetone before modification rear molecular sieve.
Fig. 2 be before modified after total acidic radical amount column diagram on adsorbent.
Fig. 3 be before modified after strong acid group quantity column diagram on adsorbent.
Fig. 4 is temperature programmed desorption (TPD) experiment flow figure.
Specific embodiment
Specific implementation of the invention is further described below in conjunction with example and accompanying drawing, but embodiments of the present invention
Not limited to this.
Embodiment 1
By lactose and water with 5g lactose：The ratio of 100mL water mixes at normal temperatures, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 1g molecular sieves：The ratio of 100ml carbodiimide solutions mixes 0.5h on agitator, will be mixed
After compound is filtered and dried, the molecular sieve that saturation has adsorbed carburization agent is obtained.In putting it into tube furnace, in nitrogen
250 DEG C are warming up under atmosphere, 2h is kept, carbonization molecular sieve is obtained after being cooled to room temperature.Carbonization molecular sieve is added to tube furnace
In, after being warming up to 200 DEG C with 2 DEG C/min under nitrogen atmosphere, gas is switched into hydrogen, continue 1h, after being cooled to room temperature, then
0.1mol/L watery hydrochloric acid is used, is 2.5g solids by solid-to-liquid ratio：100mL watery hydrochloric acid, soaks 5min, and the molecular sieve of modified treatment is mixed
After compound, then cleaned with distilled water, finally drying can obtain having good storage fragrant and sustained release performance to geranyl acetone
Adsorbent.
Embodiment 2
By lactose and water with 3g lactose：The ratio of 100mL water mixes at normal temperatures, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 3g molecular sieves：The ratio of 100ml carbodiimide solutions mixes 0.5h on agitator, will be mixed
After compound is filtered and dried, the molecular sieve that saturation has adsorbed carburization agent is obtained.In putting it into tube furnace, in nitrogen
400 DEG C are warming up under atmosphere, 0.5h is kept, carbonization molecular sieve is obtained after being cooled to room temperature.Carbonization molecular sieve is added to tubular type
In stove, after being warming up to 250 DEG C with 5 DEG C/min under nitrogen atmosphere, then gas is switched into hydrogen, continue 3h, be cooled to room temperature
Afterwards, then use 0.05mol/L watery hydrochloric acid, be 1g solids by solid-to-liquid ratio：100mL watery hydrochloric acid, soak 10min, modified treatment point
After son sieve mixture, then cleaned with distilled water, finally drying can obtain having good storage fragrant to geranyl acetone and sustained release
The adsorbent of performance.
Embodiment 3
By lactose and water with 1g lactose：The ratio of 100mL water mixes at normal temperatures, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 1.5g molecular sieves：The ratio of 100ml carbodiimide solutions mixes 0.5h on agitator, will
After mixture is filtered and dried, the molecular sieve that saturation has adsorbed carburization agent is obtained.In putting it into tube furnace, in nitrogen
Atmosphere under be warming up to 350 DEG C, keep 2.5h, obtain carbonization molecular sieve after being cooled to room temperature.Carbonization molecular sieve is added to pipe
In formula stove, after being warming up to 300 DEG C with 7 DEG C/min under nitrogen atmosphere, then gas is switched into hydrogen, continue 2h, be cooled to room
Wen Hou, then 0.01mol/L watery hydrochloric acid is used, it is 5g solids by solid-to-liquid ratio：10mL watery hydrochloric acid, soak 10min, modified treatment point
After son sieve mixture, then cleaned with distilled water, finally drying can obtain having good storage fragrant to geranyl acetone and sustained release
The adsorbent of performance.
Embodiment 4
By lactose and water with 7g lactose：The ratio of 100mL water mixes at normal temperatures, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 5g molecular sieves：The ratio of 100ml carbodiimide solutions mixes 0.5h on agitator, will be mixed
After compound is filtered and dried, the molecular sieve that saturation has adsorbed carburization agent is obtained.In putting it into tube furnace, in nitrogen
400 DEG C are warming up under atmosphere, 6h is kept, carbonization molecular sieve is obtained after being cooled to room temperature.Carbonization molecular sieve is added to tube furnace
In, after being warming up to 100 DEG C with 10 DEG C/min under nitrogen atmosphere, then gas is switched into hydrogen, continue 6h, it is cooled to room temperature
Afterwards, then use 1mol/L watery hydrochloric acid, be 3.5g solids by solid-to-liquid ratio：10mL watery hydrochloric acid, soaks 20min, the molecule of modified treatment
After sieve mixture, then cleaned with distilled water, finally drying can obtain having good storage fragrant to geranyl acetone and slow release
The adsorbent of energy.
TPD is tested：
After adsorbent saturation absorption fragrance material, following step is：(1) open gas valve 6 and be directly communicated to gas phase color
Spectrum 4, opens gas-chromatography 4, and open quality stream measuring device 1 so that flow rate of carrier gas is 30mL/min.(2) 10mg materials are taken to put
Enter in the steel pipe 3 in baking oven 2.(3) heating rate is set, the burst size that fid detector detects adsorbate is opened, treats that baseline is walked
After flat, valve is led into steel pipe, started to warm up, until adsorbate is discharged completely.Then TPD can be derived from computer 5
Spectrogram, as shown in Figure 4.
Acid and alkaline group is titrated：
After preparing NaOH, NaHCO3 solution of 0.01mol/L, take out 50mL and be added in conical flask, then add 0.1g
Adsorbent in conical flask.30 DEG C of water-baths are shaken after being well mixed within 2 days, and the particle of solution and the inside is put into centrifugation together
Centrifugation is carried out in machine and obtains supernatant liquor.The supernatant liquor of 20mL is further taken out, is added in flask.Stirrer is added toward flask
And after stirring, excess in flask is neutralized using automatical potentiometric titrimeter and with the HCl solution for configuring the 0.01mol/L for coming
Alkaline solution, finally the concentration and consumption of the addition according to HCl and NaOH, NaHCO3 can be calculated adsorbent table
The content of total acidic group and strong acid group on face.
Adsorbance is tested:
Fragrance material is adsorbed using static vapor phase method herein.The sample of 0.6g preparations is weighed in the measuring cup of 30 × 50mm
In, measuring cup is put into 12h is dried in 150 DEG C of vacuum drying chamber, after the impurity in adsorbent is fallen in removing, by dried title
Measuring bottle is put into together with adsorbent and is already equipped with the closed container of fixed fragrance material.Absorption 24h reaches at ambient temperature
To balance.
The adsorbent of 20mg is taken out from measuring cup, is put into conical flask, then again toward addition 50ml in conical flask
Absolute ethyl alcohol is then put into conical flask in water bath chader as extractant, after control temperature shakes 1h at 30 DEG C, uses
The solution for being configured with the syringe taking-up 1-2ml of filter is added in chromatogram bottle.
Chromatogram bottle is added in the automatic sampler that gas-chromatography is configured and starts detection.Chromatogram impose a condition for：Enter
Sample mouthful temperature is 200 DEG C, 150 DEG C of furnace temperature, and detector temperature is 300 DEG C.Air mass flow is 300ml/min, helium in fid detector
Gas 30ml/min, hydrogen 25ml/min.
The preparation of standard curve：Fragrance material 4g is weighed to be added in conical flask, after adding the absolute ethyl alcohol of 50mL,
Water-bath concussion 1h, produces the mother liquor for obtaining 80g/L at 30 DEG C.Then taking-up 0.5,1,2, the 4, mother liquor of 8mL is added to newly respectively
Conical flask in, and add again water-bath vibration after the absolute ethyl alcohol of 50ml be mixed to get concentration be respectively 0.8,1.6,3.2,6.4,
The titer of 12.8mg/mL.Titer is added in gas-chromatography and is detected, by calculating titer with it in chromatogram
Go out peak area ratio, obtain the standard curve of fragrance material and obtain linear regression side of the fragrance material content with peak area
Journey.
Determination sample extract, obtains the peak area of fragrance material, and spices in extract is calculated using standard curve
The concentration of material, so as to be calculated the weight of fragrance material in sorbing material.
mSpicesIt is the weight of fragrance material in sorbing material
mAdsorbentIt is the weight of sorbing material
Desorption performance is determined：
The adsorbent of adsorption saturation is put into thermogravimetric analyzer：Under 40 DEG C of constant temperatures, nitrogen flow is 30mL/
Min, purges 1h.
Desorption rate is calculated as follows：The desorption rate of essence is △ m=m1-m2, and wherein m1 is to carry out adsorbent before thermogravimetric
Weight, m2 is the weight for carrying out adsorbent after thermogravimetric, and m is the adsorbance of geranyl acetone.Finally desorption rate is：
Desorption rate=△ m/m formula 2
Keep the measure of performance：
The adsorbent of adsorption saturation is weighed, marks its quality for M1, then put it into the sealed bag of good seal
In, it is placed in drier, it is drawn off after being kept for two weeks.Its weight is weighed, labeled as M2.Calculated finally by following equation
Go out
Fig. 1 is the TPD curve maps on geranyl acetone before modification rear molecular sieve.As seen from Figure 1：In initial molecule
Two geranyl acetone desorption peaks are occurred in that in TPD spectrograms on sieve, illustrates that initial molecule sieve surface possesses two classes and can adsorb
The adsorption site of geranyl acetone；What is formed distinct contrast therewith is：When by modified several sieve samples, its spiceleaf
Only there are the relatively low desorption peaks of temperature in the TPD curves of benzylacetone, show that its strong adsorption site has disappeared, only remaining weaker
Adsorption site, it is meant that their surfaces are substantially weakened with the adhesion of geranyl acetone.And can see, existed originally
By modified, its peak value is improved, it was demonstrated that the quantity of such adsorption site is improved for desorption peaks under low temperature.
Fig. 2 be before modified after total acidic radical amount column diagram on adsorbent.As seen from Figure 2, by modified
Molecular sieve total acidic radical amount from original 1mmol/g or so, risen to 1.6-1.8mmol/g, its acidic groups
Group increases, and after this is mainly due to carbonizing and modifying, molecular sieve surface has one layer of carburization zone full of hydroxyl, therefore, its surface
Total acidic group increases.
Fig. 3 be before modified after strong acid group quantity column diagram on adsorbent.As seen from Figure 3, modified molecular screen
Strong acid group quantity be considerably less than initial molecule sieve, this mainly due to modified by surface reduction, on initial molecule sieve
Strong acid group is reduced, therefore, the strong acid group on molecular sieve surface tails off.
Table 1 is the adsorbance on geranyl acetone before modification rear molecular sieve.
Table 1
As it can be seen from table 1 adsorbance of the geranyl acetone on modified molecular screen is less than before modified.This mainly due to
Modified by carbonization and surface reduction, the structure of molecular sieve is caved in.
Table 2 is the retention rate on geranyl acetone before modification rear molecular sieve.
Table 2
| Adsorbent | Initial molecule is sieved | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Retention rate (%) | 85.23 | 90.23 | 91.28 | 93.56 | 89.73 |
From table 2 it can be seen that retention rate of the geranyl acetone on modified molecular screen improves, carried from more than original 80%
It is high to 90%.Mainly due to by modified, the total acidic group (adsorption potential) of molecular sieve surface increased.
Table 3 is the desorption rate on geranyl acetone before modification rear molecular sieve.
Table 3
| Adsorbent | Initial molecule is sieved | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Release rate (%) | 78.10 | 82.74 | 83.36 | 84.53 | 85.81 |
From table 3 it can be seen that desorption rate of the geranyl acetone on modified molecular screen has a certain degree of increase, from original
78% rise to more than 85%.Faintly acid base is largely converted into mainly due to by the strong acid group on modified molecular sieve
Group, while causing that adsorption potential number change is little on molecular sieve surface, the adsorption potential of strong adsorption is reduced, so as to improve
Release performance of the material to geranyl acetone molecule, as a result shows as geranyl acetone desorption rate on the sorbent and is carried
Rise.
Claims (10)
1. it is a kind of to preparation method of the geranyl acetone with the good adsorbent for storing up fragrant and sustained release performance, it is characterised in that bag
Include following steps：
（1）Lactose is mixed with water, lactose is dissolved in water, is produced and is obtained carbodiimide solution；
（2）Molecular sieve is added in carbodiimide solution, after stirring mixing, after mixture is filtered and dried, saturation is obtained and is inhaled
The attached molecular sieve of carburization agent；
（3）By step（2）The molecular sieve that middle saturation has adsorbed carburization agent is put into tube furnace, and carbon is carried out under the atmosphere of nitrogen
Change, carbonization molecular sieve is obtained after cooling；
（4）Carbonization molecular sieve is added in tube furnace, after first heating up under nitrogen atmosphere, then gas hydrogen is switched into, entered
Row surface reduction is modified, and is then cooled to room temperature；
（5）Use watery hydrochloric acid soaking step（4）The modified molecular screen of gained, is then cleaned with water, and finally drying can be obtained to perfume (or spice)
Phyllopodium acetone has good storage fragrant and sustained release performance adsorbent.
2. preparation method according to claim 1, it is characterised in that step（1）The lactose is with the mixed proportion of water
1-7g lactose：100mL water.
3. preparation method according to claim 1, it is characterised in that step（1）The mixing is carried out at normal temperatures.
4. preparation method according to claim 1, it is characterised in that step（2）Described in molecular sieve and carbodiimide solution
Mixing ratio is 1-5g molecular sieves:100mL carbodiimide solutions.
5. preparation method according to claim 1, it is characterised in that step（3）The temperature of middle carbonization is 200 DEG C -400
℃；The time of carbonization is 0.5-6h.
6. preparation method according to claim 1, it is characterised in that step（4）The middle surface reduction modified time is 1h-
5h。
7. preparation method according to claim 1, it is characterised in that step（4）The modified temperature of middle surface reduction is 100
DEG C -300 DEG C, heating rate is 2 DEG C/min-10 DEG C/min.
8. preparation method according to claim 1, it is characterised in that step（5）The concentration of middle watery hydrochloric acid is 0.01-
1mol/L, and it is 1-5g solids to meet modified molecular screen with the solid-to-liquid ratio of watery hydrochloric acid：10mL watery hydrochloric acid.
9. preparation method according to claim 1, it is characterised in that step（5）The time of middle immersion is 5min-20min.
10. it is a kind of obtained in the method as described in claim any one of 1-9 to have good storage fragrant to geranyl acetone and sustained release
The adsorbent of performance.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102343255A (en) * | 2010-07-29 | 2012-02-08 | 索尼公司 | Nicotine absorbent, quinoline absorbent, benzopyrene absorbent, toluidine absorbent, and carcinogen absorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102343255A (en) * | 2010-07-29 | 2012-02-08 | 索尼公司 | Nicotine absorbent, quinoline absorbent, benzopyrene absorbent, toluidine absorbent, and carcinogen absorbent |
Non-Patent Citations (2)
| Title |
|---|
| 段钰: "改性多孔材料在卷烟加香减害（CO）中的应用", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
| 熊智勇: "卷烟中香精缓释材料的研制", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
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