CN106902734B - A kind of pair of geranyl acetone has good storage perfume and adsorbent of sustained release performance and preparation method thereof - Google Patents
A kind of pair of geranyl acetone has good storage perfume and adsorbent of sustained release performance and preparation method thereof Download PDFInfo
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- CN106902734B CN106902734B CN201710105012.4A CN201710105012A CN106902734B CN 106902734 B CN106902734 B CN 106902734B CN 201710105012 A CN201710105012 A CN 201710105012A CN 106902734 B CN106902734 B CN 106902734B
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- molecular sieve
- adsorbent
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 47
- 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 37
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003860 storage Methods 0.000 title claims abstract description 20
- 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 7
- 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 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
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 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
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere 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
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 241000921313 Phyllopodium Species 0.000 claims description 3
- 235000013599 spices Nutrition 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 12
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- -1 geranyl acetones Chemical class 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000003205 fragrance Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 238000003795 desorption Methods 0.000 description 14
- 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
- 230000014759 maintenance of location Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 229960000935 dehydrated alcohol Drugs 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
- 238000004587 chromatography analysis 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
- 238000005259 measurement Methods 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
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003546 flue gas Substances 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
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000007873 sieving Methods 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration 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
Abstract
The invention discloses a kind of pair of geranyl acetones to have good storage perfume and the adsorbent of sustained release performance and preparation method thereof.Method includes the following steps: first mixing lactose at normal temperature with water, carbodiimide solution is obtained.Molecular sieve is added in carbodiimide solution again, after being stirred, mixture is filtered and is dried, obtains 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.Carbonization molecular sieve is added in tube furnace again, is heated up under nitrogen atmosphere, then gas is switched into hydrogen, surface reduction is carried out and is modified, obtain modified molecular screen.Modified molecular screen finally is impregnated with dilute 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 it to the adsorption of geranyl acetone.
Description
Technical field
The invention belongs to technical field of cigarettes more particularly to a kind of pair of geranyl acetone to have good storage fragrant and sustained release performance
Adsorbent and preparation method thereof.
Background technique
Geranyl acetone has fresh fragrance of a flower fragrance, slightly sweet tea charm, therefore geranyl acetone is passed through frequently as a kind of tool
Having the fragrance for the fresh and sweet note that can reinforce flue gas to be added into cigarette, [Yang Hongming, Yang Ganxu, Chen Jianming, et al. one kind are prominent
The essence and its application [P] .2014 in cigarette of aobvious fresh and sweet fragrant style and features].In the sustained release essence for applying to cigarette
Material needs to have essence except preferable desorption release performance, it is also necessary to have certain storage perfume (or spice) ability, so that in cigarette-opening
Flavors and fragrances is not allowed volatile after packet, and former after cigarette-opening packet are little with last several sensory differences.And existing cigarette
It is difficult to have both the two with adsorbent.
According to [a kind of ozone method of modifying of cigarette active carbon of Chen Senli, Kong Haohui, Chen Meili, et al. and application [P]
.2014 it] reports, produces a kind of cigarette active carbon using the modified method of ozone, the main surface acid by improving active carbon
Property radical amount enhance the adsorption of active carbon and fragrance, improve the retention rate of fragrance on the activated carbon to reach
Purpose, but by modified, desorption rate is not improved.And [a kind of cigarette filter adsorbent [P] .1995 of Liu Liquan]
Indefiniteness aluminosilicate adsorbent is prepared as storing up fragrant material, after discovery is volatilized 30 days in air, the retention rate of fragrance can be with
Reach 80%, but the adsorbent only considered the binding force of enhancing fragrance and adsorbent, be not involved with releasing for fragrance material
Put problem.
A kind of pair of geranyl acetone of this project main inventive has good storage fragrant and the preparation of the adsorbent of sustained release performance
Method, for solving contradiction and deficiency on fragrant for the storage of geranyl acetone fragrance in the prior art and sustained release performance, preparation
A kind of geranyl acetone stores up fragrant slow-release material out, not only has holding or improves the storage energy of adsorbent absorption geranyl acetone
Power, meanwhile, and its release performance to geranyl acetone can be improved, the potentiality with practical application.
Summary of the invention
Have good storage fragrant the present invention provides a kind of pair of geranyl acetone and adsorbent and its preparation side of sustained release performance
Method, for solving the problem of that release performance and storage fragrance can have both very well after addition fragrance in cigarette in the prior art.
The present invention is realized by following specific technical solution.
The method of the present invention includes the preparation of carbodiimide solution: lactose being mixed at normal temperature with water, lactose is made to be dissolved in water
In.The preparation of the molecular sieve of saturation absorption carburization agent: molecular sieve is added in carbodiimide solution, by being stirred certain time
Afterwards, after mixture being filtered and being dried 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
Be carbonized molecular sieve.Surface reduction is modified: carbonization molecular sieve being added in tube furnace, is heated up under nitrogen atmosphere, then by gas
Hydrogen is switched to, it is modified to carry out surface reduction at high temperature.Impurity is precipitated: impregnating modified molecular screen with a certain amount of dilute hydrochloric acid,
Again with after distilled water, it is dried to obtain required sample.
A kind of pair of geranyl acetone has good storage fragrant and the preparation method of the adsorbent of sustained release performance, including following step
It is rapid:
(1) lactose is mixed with water, is dissolved in water lactose, produce to obtain carbodiimide solution；
(2) molecular sieve is added in carbodiimide solution, after being stirred, after mixture is filtered and dried, is satisfied
With the molecular sieve for having adsorbed carburization agent；
(3) saturation has adsorbed carburization agent in step (2) molecular sieve is put into tube furnace, under the atmosphere of nitrogen into
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, is then cooled to room temperature；
(5) dilute hydrochloric acid soaking step (4) resulting modified molecular screen is used, is then washed with water, finally drying can be obtained
Have good storage fragrant geranyl acetone and the adsorbent of sustained release performance.
Preferably, the mixed proportion of step (1) lactose and water is 1-7g lactose: 100mL water.
Preferably, step (1) mixing carries out at normal temperature.
Preferably, the mixing ratio of molecular sieve described in step (2) and carbodiimide solution is 1-5g molecular sieve: 100mL carbodiimide solution.
Preferably, the temperature being carbonized in step (3) is 200 DEG C -400 DEG C.
Preferably, the time being carbonized in step (3) is 0.5-6h.
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 dilute hydrochloric acid is 0.01-1mol/L in step (5), and meets modified molecular sieve and dilute hydrochloric acid
Solid-to-liquid ratio be 1-5g solid: 10mL hydrochloric acid.
Preferably, the time impregnated in step (5) is 5min-20min.
Preferably, a kind of pair of geranyl acetone has good storage fragrant and the preparation method of the adsorbent of sustained release performance, including
Following steps:
(1) by lactose and water with 1-7g lactose: the ratio of 100mL water mixes at normal temperature, is dissolved in water lactose, system
Obtain carbodiimide solution；
(2) by molecular sieve and carbodiimide solution with 1-5g molecular sieve: the ratio of 100mL carbodiimide solution is mixed, and fills molecular sieve
Divide the lactose in absorption carbodiimide solution, then, after filtering and drying at high temperature, obtains 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, is warming up to 100 DEG C -300 under nitrogen atmosphere
After DEG C, it is passed through hydrogen stream, continues 1h-5h, is then cooled to room temperature；
(5) 0.01mol/L-1mol/L dilute hydrochloric acid is used again, is 1-5g solid: the ratio of 10mL hydrochloric acid in solid-to-liquid ratio, is impregnated
After the molecular sieve mixture of hydrogen reducing processing, wash with distilled water, finally dry can be obtained has geranyl acetone
The adsorbent of good storage perfume and sustained release performance.
Compared with prior art, the invention has the following advantages:
On the one hand adsorbent prepared by the present invention has 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, weakens it to the adsorption of geranyl acetone.The long and is: it is modified,
Absorption bit quantity does not change, and adsorption is weakened, and effectively discharges perfume under the premise of adsorbance is constant to realize
The performance of phyllopodium acetone.
Detailed description of the invention
Fig. 1 is the TPD curve graph on geranyl acetone before modification rear molecular sieve.
Fig. 2 is the total acidic radical amount column diagram on rear adsorbent before modified.
Fig. 3 is the strong acid group quantity column diagram on rear adsorbent before modified.
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 attached drawing, but embodiments of the present invention
It is without being limited thereto.
Embodiment 1
By lactose and water with 5g lactose: the ratio of 100mL water mixes at normal temperature, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 1g molecular sieve: the ratio of 100ml carbodiimide solution mixes 0.5h on blender, will mix
After conjunction object is filtered and dries, the molecular sieve that saturation has adsorbed carburization agent is obtained.It puts it into tube furnace, in nitrogen
It is warming up to 250 DEG C under atmosphere, keeps 2h, 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 under nitrogen atmosphere with 2 DEG C/min, gas is switched into hydrogen, continues 1h, after being cooled to room temperature, then
It is 2.5g solid: 100mL dilute hydrochloric acid by solid-to-liquid ratio with 0.1mol/L dilute hydrochloric acid, impregnates 5min, the molecular sieve of modified processing is mixed
After closing object, then wash with distilled water, finally drying can be obtained fragrant and sustained release performance with well storing up to geranyl acetone
Adsorbent.
Embodiment 2
By lactose and water with 3g lactose: the ratio of 100mL water mixes at normal temperature, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 3g molecular sieve: the ratio of 100ml carbodiimide solution mixes 0.5h on blender, will mix
After conjunction object is filtered and dries, the molecular sieve that saturation has adsorbed carburization agent is obtained.It puts it into tube furnace, in nitrogen
It is warming up to 400 DEG C under atmosphere, keeps 0.5h, carbonization molecular sieve is obtained after being cooled to room temperature.Carbonization molecular sieve is added to tubular type
In furnace, after being warming up to 250 DEG C under nitrogen atmosphere with 5 DEG C/min, then gas switched into hydrogen, continues 3h, be cooled to room temperature
Afterwards, then with 0.05mol/L dilute hydrochloric acid, it is 1g solid: 100mL dilute hydrochloric acid by solid-to-liquid ratio, impregnates 10min, point of modified processing
After son sieve mixture, then wash with distilled water, finally dry can be obtained has good storage fragrant and sustained release geranyl acetone
The adsorbent of performance.
Embodiment 3
By lactose and water with 1g lactose: the ratio of 100mL water mixes at normal temperature, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 1.5g molecular sieve: the ratio of 100ml carbodiimide solution mixes 0.5h on blender, will
After mixture is filtered and dries, the molecular sieve that saturation has adsorbed carburization agent is obtained.It puts it into tube furnace, in nitrogen
Atmosphere under be warming up to 350 DEG C, keep 2.5h, carbonization molecular sieve obtained after being cooled to room temperature.Carbonization molecular sieve is added to pipe
In formula furnace, after being warming up to 300 DEG C under nitrogen atmosphere with 7 DEG C/min, then gas switched into hydrogen, continues 2h, be cooled to room
Wen Hou, then be 5g solid: 10mL dilute hydrochloric acid by solid-to-liquid ratio with 0.01mol/L dilute hydrochloric acid, impregnate 10min, point of modified processing
After son sieve mixture, then wash with distilled water, finally dry can be obtained has good storage fragrant and sustained release geranyl acetone
The adsorbent of performance.
Embodiment 4
By lactose and water with 7g lactose: the ratio of 100mL water mixes at normal temperature, is dissolved in water lactose, produces
To carbodiimide solution；By molecular sieve and carbodiimide solution with 5g molecular sieve: the ratio of 100ml carbodiimide solution mixes 0.5h on blender, will mix
After conjunction object is filtered and dries, the molecular sieve that saturation has adsorbed carburization agent is obtained.It puts it into tube furnace, in nitrogen
It is warming up to 400 DEG C under atmosphere, keeps 6h, 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 under nitrogen atmosphere with 10 DEG C/min, then gas switched into hydrogen, continues 6h, be cooled to room temperature
Afterwards, then with 1mol/L dilute hydrochloric acid, it is 3.5g solid: 10mL dilute hydrochloric acid by solid-to-liquid ratio, impregnates 20min, the molecule of modified processing
After sieving mixture, then wash with distilled water, finally dry can be obtained has good storage fragrant and slow release geranyl acetone
The adsorbent of energy.
TPD test:
After adsorbent saturation absorption fragrance material, following step are as follows: (1) open gas valve 6 and be directly communicated to gas phase color
Spectrum 4 opens gas-chromatography 4, and opens quality stream measuring device 1, so that flow rate of carrier gas is 30mL/min.(2) 10mg material is taken to put
Enter in the steel pipe 3 in baking oven 2.(3) heating rate is set, the burst size of fid detector detection adsorbate is opened, is walked to baseline
After flat, valve is led into steel pipe, is started to warm up, until adsorbate releases completely.Then TPD can be exported from computer 5
Spectrogram, as shown in Figure 4.
Acid and alkaline group titration:
After NaOH, NaHCO3 solution for preparing 0.01mol/L, takes out 50mL and be added in conical flask, then add 0.1g
Adsorbent into conical flask.30 DEG C of water-baths shake 2 days after mixing, and the particle of solution and the inside is put into togerther centrifugation
Centrifugation is carried out in machine obtains supernatant liquor.The supernatant liquor for further taking out 20mL, is added in flask.Stirrer is added into flask
And after stirring, excess is neutralized in flask using automatical potentiometric titrimeter and with the HCl solution for configuring the 0.01mol/L come
Alkaline solution, adsorbent table finally can be calculated according to the concentration and dosage of the additive amount of HCl and NaOH, NaHCO3
The content of total acidic group and strong acid group on face.
Adsorbance test:
Fragrance material is adsorbed using static vapor phase method herein.The sample of 0.6g preparation is weighed in the weighing bottle of 30 × 50mm
In, weighing bottle is put into 150 DEG C of vacuum oven and dries 12h, after the impurity in adsorbent is fallen in removing, by the title after drying
Measuring bottle and adsorbent are put into togerther in the closed container for being already equipped with fixed fragrance material.It adsorbs and reaches for 24 hours at room temperature
To balance.
The adsorbent that 20mg is taken out from weighing bottle, is put into conical flask, is then added 50ml's into conical flask again
Dehydrated 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 that syringe configured with filter takes out 1-2ml is added in chromatogram bottle.
Chromatogram bottle is added in the configured autosampler of gas-chromatography and starts to detect.Chromatography imposes a condition are as follows: into
Sample mouth temperature is 200 DEG C, and 150 DEG C of furnace temperature, 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: weighing fragrance material 4g and be added in conical flask, after adding the dehydrated alcohol of 50mL,
1h is shaken in water-bath at 30 DEG C, produces the mother liquor for obtaining 80g/L.Then take out 0.5 respectively, 1,2,4, the mother liquor of 8mL is added to newly
Conical flask in, and add again water-bath oscillation after the dehydrated alcohol of 50ml be mixed to get concentration be respectively 0.8,1.6,3.2,6.4,
12.8mg/mL titer.Titer is added in gas-chromatography and is detected, by calculate titer with it in chromatography
Go out peak area ratio, obtain the standard curve of fragrance material and obtain fragrance material content with the linear regression side of peak area
Journey.
Sample extraction liquid is measured, the peak area of fragrance material is obtained, fragrance in extract liquor is calculated using standard curve
The concentration of substance, so that the weight of fragrance material in adsorbent material be calculated.
mFragranceFor the weight of fragrance material in adsorbent material
mAdsorbentFor the weight of adsorbent material
Desorption performance measurement:
The adsorbent of adsorption saturation is put into thermogravimetric analyzer: under 40 DEG C of constant temperatures, nitrogen flow 30mL/
Min purges 1h.
The calculating of desorption rate is as follows: the desorption rate of essence is △ m=m1-m2, and wherein m1 is to carry out adsorbent before thermogravimetric
Weight, m2 are the weight of adsorbent after carrying out thermogravimetric, and m is the adsorbance of geranyl acetone.Last desorption rate are as follows:
Desorption rate=△ m/m formula 2
The measurement of retention property:
The adsorbent for weighing adsorption saturation, marking its quality is M1, then puts it into the sealed bag being sealed
In, it is placed in drier, is drawn off after being kept for two weeks.Its weight is weighed, M2 is labeled as.It is calculated finally by following equation
Out
Fig. 1 is the TPD curve graph on geranyl acetone before modification rear molecular sieve.As seen from Figure 1: in initial molecule
Occur two geranyl acetone desorption peaks in TPD spectrogram on sieve, illustrates that initial molecule sieve surface possesses two classes and can adsorb
The adsorption site of geranyl acetone；Form distinct contrast therewith: when by modified several sieve samples, spiceleaf
Only there are the lower desorption peaks of temperature in the TPD curve of benzylacetone, shows that its strong adsorption site has disappeared, only remaining weaker
Adsorption site, it is meant that the binding force of their surfaces and geranyl acetone is obviously weakened.And can see, existed originally
Desorption peaks under low temperature are by modified, and peak value is improved, it was demonstrated that the quantity of such adsorption site is improved.
Fig. 2 is the total acidic radical amount column diagram on rear adsorbent before modified.As seen from Figure 2, process is modified
Molecular sieve total acidic radical amount from original 1mmol/g or so, risen to 1.6-1.8mmol/g, acidic groups
Group increases, and after this is mainly due to carbonizing and modifying, molecular sieve surface has one layer of carburization zone for being full of hydroxyl, therefore, surface
Total acidic group increases.
Fig. 3 is the strong acid group quantity column diagram on rear adsorbent before modified.As seen from Figure 3, modified molecular screen
Strong acid group quantity be considerably less than initial molecule sieve, this mainly due to by surface reduction it is modified, initial molecule sieve on
Strong acid group is reduced, and 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 collapsed.
Table 2 is the retention rate on geranyl acetone before modification rear molecular sieve.
Table 2
| Adsorbent | Initial molecule sieve | 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, mentioned from more than original 80%
Height is to 90%.Mainly due to by modified, the total acidic group (adsorption potential) of molecular sieve surface is increased.
Table 3 is the desorption rate on geranyl acetone before modification rear molecular sieve.
Table 3
| Adsorbent | Initial molecule sieve | 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 degree of increase, from original
78% rise to 85% or more.Faintly acid base is largely converted into mainly due to by the strong acid group on modified molecular sieve
Group, cause to adsorb on molecular sieve surface bit quantity variation it is little while, the adsorption potential of strong adsorption is reduced, to improve
Release performance of the material to geranyl acetone molecule, as a result shows as the desorption rate of geranyl acetone on the sorbent and is mentioned
It rises.
Claims (10)
1. a kind of pair of geranyl acetone has good storage fragrant and the preparation method of the adsorbent of sustained release performance, which is characterized in that packet
Include following steps:
(1) lactose is mixed with water, is dissolved in water lactose, produce to obtain carbodiimide solution；
(2) molecular sieve is added in carbodiimide solution, after being stirred, after mixture is filtered and dried, obtains saturation and inhale
The attached molecular sieve of carburization agent；
(3) molecular sieve that saturation has adsorbed carburization agent in step (2) is put into tube furnace, 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 is switched into hydrogen, into
Row surface reduction is modified, is then cooled to room temperature；
(5) dilute hydrochloric acid soaking step (4) resulting modified molecular screen is used, is then washed with water, finally drying can be obtained to perfume (or spice)
Phyllopodium acetone has good storage fragrant and the adsorbent of sustained release performance；
The modified temperature of surface reduction is 100 DEG C -300 DEG C in step (4).
2. preparation method according to claim 1, which is characterized in that the mixed proportion of step (1) lactose and water is
1-7g lactose: 100mL water.
3. preparation method according to claim 1, which is characterized in that step (1) mixing carries out at normal temperature.
4. preparation method according to claim 1, which is characterized in that molecular sieve described in step (2) and carbodiimide solution
Mixing ratio is 1-5g molecular sieve: 100mL carbodiimide solution.
5. preparation method according to claim 1, which is characterized in that the temperature being carbonized in step (3) is 200 DEG C -400
℃；The time of carbonization is 0.5-6h.
6. preparation method according to claim 1, which is characterized in that the surface reduction modified time is 1h- in step (4)
5h。
7. preparation method according to claim 1, which is characterized in that the modified heating rate of surface reduction in step (4)
For 2 DEG C/min-10 DEG C/min.
8. preparation method according to claim 1, which is characterized in that the concentration of dilute hydrochloric acid is 0.01- in step (5)
1mol/L, and the solid-to-liquid ratio for meeting modified molecular screen and dilute hydrochloric acid is 1-5g solid: 10mL dilute hydrochloric acid.
9. preparation method according to claim 1, which is characterized in that the time impregnated in step (5) is 5min-20min.
10. a kind of pair of geranyl acetone as made from the described in any item methods of claim 1-9 has good storage fragrant and sustained release
The adsorbent of performance.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| 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 |
|---|
| 卷烟中香精缓释材料的研制;熊智勇;《中国优秀硕士学位论文全文数据库（电子期刊）》;20140515(第5期);B018-37 * |
| 改性多孔材料在卷烟加香减害（CO）中的应用;段钰;《中国优秀硕士学位论文全文数据库（电子期刊）》;20160215(第2期);B024-502 * |
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