CN108187603A - A kind of modified phosphate aluminum molecular screen material and preparation method and application - Google Patents
A kind of modified phosphate aluminum molecular screen material and preparation method and application Download PDFInfo
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- CN108187603A CN108187603A CN201810004560.2A CN201810004560A CN108187603A CN 108187603 A CN108187603 A CN 108187603A CN 201810004560 A CN201810004560 A CN 201810004560A CN 108187603 A CN108187603 A CN 108187603A
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- Prior art keywords
- crapo
- cigarette
- preparation
- boehmite
- main flume
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims description 18
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 71
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 65
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 17
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 17
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 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 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract 3
- 230000004048 modification Effects 0.000 claims abstract 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- -1 boehmite2O3 Chemical compound 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 229940001007 aluminium phosphate Drugs 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003546 flue gas Substances 0.000 abstract description 6
- 239000011651 chromium Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000779 smoke Substances 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000391 smoking effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 4
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 description 1
- 108050008072 Cytochrome c oxidase subunit IV Proteins 0.000 description 1
- FLAQQSHRLBFIEZ-UHFFFAOYSA-N N-Methyl-N-nitroso-4-oxo-4-(3-pyridyl)butyl amine Chemical compound O=NN(C)CCCC(=O)C1=CC=CN=C1 FLAQQSHRLBFIEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Modification phosphate aluminium molecular sieve material the invention discloses hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume and preparation method and application.By adding triethylamine template, using chromic nitrate as chromium source, boehmite is silicon source, and phosphoric acid is phosphorus source, and CrAPO 5 is synthesized using hydro-thermal method.The material first Application is in cigarette filter rod, and alternative reduces the hydrocyanic acid release amount 53.29% in cigarette mainstream flue gas, to the reduced rate unobvious of other gas burst sizes in cigarette mainstream flue gas.Compared on going result, additive amount is few, can realize efficiently drop evil, have good application value.
Description
Technical field
The present invention relates to a kind of modified phosphate aluminum molecular screen materials and preparation method and application, and in particular to a kind of to select
Selecting property reduces modified phosphate aluminum molecular screen material of determination of hydrogen cyanide in mainstream cigarette smoke burst size and preparation method and application, belongs to
In cigarette material preparing technical field.
Background technology
As people are to the growing interest smoked with health problem, the harmful components in cigarette, the suction for improving cigarette are reduced
Eating safety becomes the emphasis of tobacco business research work.Domestic tobacco business has carried out into one the substance in Huffman inventory
Step is clear and definite, and State Bureau points out CO, HCN, NNK, NH3, 7 kinds of benzo [a] pyrene, phenol and crotonaldehyde harmful components burst sizes can be effective
Characterize cigarette mainstream flue gas biohazardous.For further Development of Tobacco, the volume of low tar, less harmful is researched and developed
Cigarette is the top priority of current enterprise.
Hydrogen cyanide（HCN）It is a kind of colourless poisonous gas or liquid with semen armeniacae amarae taste, low boiling point, volatile, room temperature
Under exist in gaseous form, can by all means it is oral or nasal sucking make one to be poisoned, hydrogen cyanide is soluble easily in water, ethyl alcohol, micro-
Ether is dissolved in, aqueous is in faintly acid, belongs to the extremely toxic substance of high volatile, and intoxication mainly passes through CN-Occur.Hydrogen in cigarette
Cyanic acid is mainly derived from nitrate and nitrogenous compound in tobacco（Such as amino acid, protein）Oxidation point during burning and sucking
Solution, burst size are about 30-300 μ g/ branch, and the hydrogen cyanide in flue gas is sucked through respiratory tract, can be with internal high swage cell color
Plain oxidizing ferment, which combines, becomes cyaniding high ferro shape cytochrome oxidase, loses the effect for transmitting oxygen, causes histanoxia and be poisoned,
Harm is generated to the health of people.Therefore, exploitation can effectively reduce the material of determination of hydrogen cyanide in mainstream cigarette smoke burst size
To improving smoking property of cigarette safety, protection human health is of great significance.
At present, the removal for hydrogen cyanide micro in cigarette mainstream flue gas both at home and abroad, it is more using absorption method and catalysis oxygen
Change method.Ammonium carboxylate salt made from the primary amine or secondary amine of alkyl or hydroxyalkyl and carboxylic acid reaction is dispersed in by US3410282 can make cigarette
Gas by carrier on, the HCN in selectively removing cigarette smoke.CN1462652A etc. elaborates that catalytic oxidation is reducing volume
Effect in cigarette in hydrogen cyanide shows higher catalytic activity.But production cost is higher, and in process of production, meeting
Have and be unevenly distributed phenomenon in single cigarette, it is difficult to control.
Invention content
In view of the defects existing in the prior art, the present invention provides hydrogen cyanide in a kind of energy selectivity reducing cigarette main flume
Modified phosphate aluminum molecular screen material of burst size and preparation method and application.
The purpose of the present invention is achieved through the following technical solutions：
The preparation side of the modified phosphate aluminum molecular screen material of hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with water in boehmite, later by chromic nitrate water dissolution
Afterwards, it is added in boehmite suspension, is stirred in suspension；Later, it under stirring, is added dropwise
Volumetric concentration is 80~85% phosphoric acid, and after continuing 0.9~1.1h of stirring after adding, three second are added dropwise in the state of stirring
Amine continues 1.9~2.1h of stirring after adding, obtain CrAPO-5 Primogels；
Wherein, the Al in chromic nitrate, boehmite2O3、H3PO4, triethylamine and water the molar ratio of total dosage be n:(1-n):
1:0.74~0.76:M, wherein n=0.03~0.09, m=1.00~1.22；Total dosage of the water is institute in boehmite
The amount of the crystallization water contained, the amount that boehmite is made to water used in suspension with by the amount of chromic nitrate dissolving water used it
With.
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels that prepare add in using polytetrafluoroethylene (PTFE) as
It in the reaction kettle of liner, at 180~200 DEG C after 24~48h of crystallization, takes out and is rapidly cooled to room temperature, wash 2 ~ 5 later
It is secondary, be placed in 118~122 DEG C of baking ovens dry 7.5~8.5h, take out, wear into fine powder to 100 mesh, finally by fine powder 450~
650 DEG C of Muffle 4~6h of kiln roasting, obtains CrAPO-5, i.e., hydrogen cyanide in described energy selectivity reducing cigarette main flume
The modified phosphate aluminum molecular screen material of burst size.
The present invention also provides hydrogen cyanide in the energy selectivity reducing cigarette main flume as made from the preparation method to discharge
The modified phosphate aluminum molecular screen material C rAPO-5 of amount.CrAPO-5 mesoporous pore sizes obtained are 5-8nm, and specific surface area is not less than
200m2/g。
The present invention also provides hydrogen cyanide in the energy selectivity reducing cigarette main flume as made from the preparation method to discharge
Applications of the modified phosphate aluminum molecular screen material C rAPO-5 of amount as cigarette filter-tip additive agent.
Preferably, CrAPO-5 is added in the middle part of cigarette filter.
XRD tests are done to CrAPO-5 obtained, test spectrogram is as shown in Figure 2.The XRD of CrAPO-5 as can be seen from Figure 2
There is characteristic peak and corresponds to crystal face in 2 θ=100 °, 20 °, 34 °, 56 °, 59 °, 69 °, 36 ° and 23 ° in spectrogram（100）、（211）、
（002）、（200）、（110）、（220）、（311）、（400）It is completely the same with the characteristic peak of APO-5, illustrate metal heteroatom lattice
Original phosphate aluminium molecular sieve skeleton is not destroyed after aluminium on substitution skeleton in AFI topological structures.Table 1 is by cell parameter
The data being calculated, it can be seen that the unit cell volume increase of APO-5 compared with the unit cell volume of CrAPO-5, and in figure simultaneously
There is no the appearance of the peak of metal and metal oxide, this illustrates metals to be successfully doped in skeleton.
1 molecular sieve cell parameter of table and unit cell volume
The metal state in XPS measure framework of molecular sieve is carried out to CrAPO-5, Fig. 3 is the XPS spectrum figure of CrAPO-5.It is combined in figure
Can be Cr for the characteristic peak of 574.6eV and 584.3eV3+Characteristic peak, illustrate prepare CrAPO-5 on be successfully loaded with Cr member
Element, and with Cr3+Form exist.Instead of the part Al and P on skeleton after on metallic element introducing APO-5, replace Al3+And
Its acidity is not interfered with, and P is+5 valencys, by Cr3+It has extra active sites after substitution to vacate, so as to adsorb the stronger hydrogen of polarity
Cyanic acid.
Nitrogen adsorption-desorption test analysis is carried out to CrAPO-5, Fig. 4 is nitrogen adsorption-desorption of CrAPO-5 molecular sieves
Curve and graph of pore diameter distribution, it is seen that adsorption desorption balanced line is 0.3<P/P0<Standard is presented in 0.9 pressure limit
IV type hysteresis loop, illustrate two kinds of materials for the uniform mesoporous material in aperture.The mesoporous channel of the offer of CrAPO-5 molecular sieves can
To allow the entrance of hydrogen cyanide, it is possible to physical absorption hydrogen cyanide.
With respect to current material, the invention has the advantages that：
1st, modified phosphate aluminum molecular screen material prepared by the present invention has loose, porous cavity structure, has larger specific surface
Product, every cigarette addition 20mg CrAPO-5 can effectively reduce the hydrogen cyanide in cigarette smoke, can be maximized in same attribute material
Reduction hydrogen cyanide, and the cambridge filter after infrared test adsorbs do not find CrAPO-5 sieve components, illustrates this
Material has good safety；
2nd, preparation method of the present invention belongs to hydrothermal synthesis method, and the iron that Cr atoms enter APO-5 skeletons is carried as lattice substitution
Load, i.e., aluminum-oxygen tetrahedron in the coordination tetrahedron of generating portion chromium metal and oxygen substitution skeleton in framework of molecular sieve；
3rd, the present invention is modified APO-5 molecular sieves using lattice method of substitution, and APO-5 changes electronegativity after Cr is added in, this is sent out
Bright material is used in cigarette filter after preparing composite filter tip, can effectively reduce the burst size of the HCN in cigarette mainstream flue gas, highest
Its burst size 43.73% can be reduced；
4th, the lower cost for material, safe and reliable, method is simple, has reliable commercial Application.
Description of the drawings
Fig. 1 is the scanning electron microscope of CrAPO-5 prepared by embodiment 5（SEM）Figure；
The XRD spectra of CrAPO-5 that Fig. 2 is APO-5 and prepared by embodiment 5；
Fig. 3 is the XPS spectrum figure of CrAPO-5 prepared by embodiment 5；
Fig. 4 is physical absorption-desorption curve of CrAPO-5 prepared by embodiment 5.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and it should not be regarded as limiting this hair
Bright range.In the examples where no specific technique or condition is specified, according to the described technology of document in the art or condition
Or it is carried out according to product description.Reagents or instruments used without specified manufacturer, being can be by buying what is obtained
Conventional products.
Embodiment 1
The preparation side of the modified phosphate aluminum molecular screen material of hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with distilled water in boehmite, later steams chromic nitrate
After distilled water dissolving, it is added in boehmite suspension, is stirred in suspension；Later, under stirring,
The phosphoric acid that volumetric concentration is 80% is added dropwise, continues after adding after stirring 1h, triethylamine is added dropwise in the state of stirring,
Continue to stir 1.9h after adding, obtain CrAPO-5 Primogels；
Wherein, the Al in chromic nitrate, boehmite2O3、H3PO4, triethylamine and water the molar ratio of total dosage be 0.03:
0.97:1:0.75:1.00；
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels prepared are added in using polytetrafluoroethylene (PTFE) as liner
Reaction kettle in, at 200 DEG C after crystallization 36h, take out and ice water used to be rapidly cooled to room temperature, later using deionized water
Washing 2 times is placed in 118 DEG C of baking ovens dry 8.5h, takes out, wear into fine powder to 100 mesh using agate mortar, finally fine powder exists
550 DEG C of Muffle kiln roasting 6h, obtains CrAPO-5, can hydrocyanic acid release amount in selectivity reducing cigarette main flume
Modified phosphate aluminium molecular sieve filter tip adsorption material.
The CrAPO-5 being prepared is added in the middle part of the acetic acid filter tip of cigarette, addition is 20mg/ branch, and not add
Enter the blank cigarette of CrAPO-5 as control, each 6 cigarette of sample test, and one group of Duplicate Samples is set, filtered with built-in Cambridge
The trap of piece collects smoke components.It is needed before experiment by all samples and cambridge filter in temperature（20±2）DEG C, humidity（60±
2）48h is placed in the constant temperature and humidity tandem-driving bogie of %, using the linear smoking machine of Britain Si Rulin CERULEANSM450 types, according to
Method as defined in GB/T19609-2004 measures the content by ammonia, HCN in cigarette smoke after filter tip respectively, the results are shown in Table 2.
Table 2
。
Embodiment 2
The preparation side of the modified phosphate aluminum molecular screen material of hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with distilled water in boehmite, later steams chromic nitrate
After distilled water dissolving, it is added in boehmite suspension, is stirred in suspension；Later, under stirring,
The phosphoric acid that volumetric concentration is 82% is added dropwise, continues after adding after stirring 0.9h, three second is added dropwise in the state of stirring
Amine continues to stir 1.9h after adding, obtains CrAPO-5 Primogels；
Wherein, the Al in chromic nitrate, boehmite2O3、H3PO4, triethylamine and water the molar ratio of total dosage be 0.03:
0.97:1:0.74:1.10；
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels prepared are added in using polytetrafluoroethylene (PTFE) as liner
Reaction kettle in, at 200 DEG C after crystallization 36h, take out and ice water used to be rapidly cooled to room temperature, later using deionized water
Washing 5 times is placed in 120 DEG C of baking ovens dry 8h, takes out, wear into fine powder to 100 mesh using agate mortar, finally fine powder exists
550 DEG C of Muffle kiln roasting 5h, obtains CrAPO-5, can hydrocyanic acid release amount in selectivity reducing cigarette main flume
Modified phosphate aluminium molecular sieve filter tip adsorption material.
The CrAPO-5 being prepared is added in the middle part of the acetic acid filter tip of cigarette, addition is 20mg/ branch, and not add
Enter the blank cigarette of CrAPO-5 as control, each 6 cigarette of sample test, and one group of Duplicate Samples is set, filtered with built-in Cambridge
The trap of piece collects smoke components.It is needed before experiment by all samples and cambridge filter in temperature（20±2）DEG C, humidity（60±
2）48h is placed in the constant temperature and humidity tandem-driving bogie of %, using the linear smoking machine of Britain Si Rulin CERULEANSM450 types, according to
Method as defined in GB/T19609-2004 measures the content by ammonia, HCN in cigarette smoke after filter tip respectively, the results are shown in Table 3.
Table 3
。
Embodiment 3
The preparation side of the modified phosphate aluminum molecular screen material of hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with distilled water in boehmite, later steams chromic nitrate
After distilled water dissolving, it is added in boehmite suspension, is stirred in suspension；Later, under stirring,
The phosphoric acid that volumetric concentration is 83% is added dropwise, continues after adding after stirring 1h, triethylamine is added dropwise in the state of stirring,
Continue to stir 1.9h after adding, obtain CrAPO-5 Primogels；
Wherein, the Al in chromic nitrate, boehmite2O3、H3PO4, triethylamine and water the molar ratio of total dosage be 0.03:
0.97:1:0.75:1.11；
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels prepared are added in using polytetrafluoroethylene (PTFE) as liner
Reaction kettle in, at 180 DEG C after crystallization 48h, take out and ice water used to be rapidly cooled to room temperature, later using deionized water
Washing 2 times is placed in 121 DEG C of baking ovens dry 8h, takes out, wear into fine powder to 100 mesh using agate mortar, finally fine powder exists
650 DEG C of Muffle kiln roasting 4h, obtains CrAPO-5, can hydrocyanic acid release amount in selectivity reducing cigarette main flume
Modified phosphate aluminium molecular sieve filter tip adsorption material.
The CrAPO-5 being prepared is added in the middle part of the acetic acid filter tip of cigarette, addition is 20mg/ branch, and with to add
Enter the blank cigarette of CrAPO-5 as control, each 6 cigarette of sample test, and one group of Duplicate Samples is set, filtered with built-in Cambridge
The trap of piece collects smoke components.It is needed before experiment by all samples and cambridge filter in temperature（20±2）DEG C, humidity（60±
2）48h is placed in the constant temperature and humidity tandem-driving bogie of %, using the linear smoking machine of Britain Si Rulin CERULEANSM450 types, according to
Method as defined in GB/T19609-2004 measures the content by ammonia, HCN in cigarette smoke after filter tip respectively, the results are shown in Table 4.
Table 4
。
Embodiment 4
The preparation side of the modified phosphate aluminum molecular screen material of hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with distilled water in boehmite, later steams chromic nitrate
After distilled water dissolving, it is added in boehmite suspension, is stirred in suspension；Later, under stirring,
The phosphoric acid that volumetric concentration is 85% is added dropwise, continues after adding after stirring 1.1h, three second is added dropwise in the state of stirring
Amine continues to stir 2.1h after adding, obtains CrAPO-5 Primogels；
Wherein, the Al in chromic nitrate, boehmite2O3、H3PO4, triethylamine and water the molar ratio of total dosage be 0.06:
0.94:1:0.75:1.22；
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels prepared are added in using polytetrafluoroethylene (PTFE) as liner
Reaction kettle in, at 190 DEG C crystallization for 24 hours after, take out and ice water used to be rapidly cooled to room temperature, later using deionized water
Washing 2 times is placed in 122 DEG C of baking ovens dry 7.5h, takes out, wear into fine powder to 100 mesh using agate mortar, finally fine powder exists
450 DEG C of Muffle kiln roasting 6h, obtains CrAPO-5, can hydrocyanic acid release amount in selectivity reducing cigarette main flume
Modified phosphate aluminium molecular sieve filter tip adsorption material.
The CrAPO-5 being prepared is added in the middle part of the acetic acid filter tip of cigarette, addition is 20mg/ branch, and not add
Enter the blank cigarette of CrAPO-5 as control, each 6 cigarette of sample test, and one group of Duplicate Samples is set, filtered with built-in Cambridge
The trap of piece collects smoke components.It is needed before experiment by all samples and cambridge filter in temperature（20±2）DEG C, humidity（60±
2）48h is placed in the constant temperature and humidity tandem-driving bogie of %, using the linear smoking machine of Britain Si Rulin CERULEANSM450 types, according to
Method as defined in GB/T19609-2004 measures the content by ammonia, HCN in cigarette smoke after filter tip respectively, the results are shown in Table 5.
Table 5
。
Embodiment 5
The preparation side of the modified phosphate aluminum molecular screen material of hydrocyanic acid release amount in a kind of energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with distilled water in boehmite, later steams chromic nitrate
After distilled water dissolving, it is added in boehmite suspension, is stirred in suspension；Later, under stirring,
The phosphoric acid that volumetric concentration is 85% is added dropwise, continues after adding after stirring 1.1h, three second is added dropwise in the state of stirring
Amine continues to stir 2h after adding, obtains CrAPO-5 Primogels；
Wherein, the Al in chromic nitrate, boehmite2O3、H3PO4, triethylamine and water the molar ratio of total dosage be 0.09:
0.91:1:0.76:1.11；
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels prepared are added in using polytetrafluoroethylene (PTFE) as liner
Reaction kettle in, at 190 DEG C after crystallization 36h, take out and ice water used to be rapidly cooled to room temperature, later using deionized water
Washing 3 times is placed in 120 DEG C of baking ovens dry 8h, takes out, wear into fine powder to 100 mesh using agate mortar, finally fine powder exists
450 DEG C of Muffle kiln roasting 5h, obtains CrAPO-5, i.e., modified phosphate aluminium molecular sieve filter tip adsorption material.
The scanning electron microscope of CrAPO-5 obtained（SEM）Figure is as shown in Figure 1, with the XRD spectra of APO-5 as shown in Fig. 2, XPS
Spectrogram is as shown in figure 3, physical absorption-desorption curve is as shown in Figure 4.
The CrAPO-5 being prepared is added in the middle part of the acetic acid filter tip of cigarette, addition is 20mg/ branch, and not add
Enter the blank cigarette of CrAPO-5 as control, each 6 cigarette of sample test, and one group of Duplicate Samples is set, filtered with built-in Cambridge
The trap of piece collects smoke components.It is needed before experiment by all samples and cambridge filter in temperature（20±2）DEG C, humidity（60±
2）48h is placed in the constant temperature and humidity tandem-driving bogie of %, using the linear smoking machine of Britain Si Rulin CERULEANSM450 types, according to
Method as defined in GB/T19609-2004 measures the content by ammonia, HCN in cigarette smoke after filter tip respectively, the results are shown in Table 6；
Table 6
。
Claims (5)
1. a kind of preparation side of the modification phosphate aluminium molecular sieve material of hydrocyanic acid release amount in energy selectivity reducing cigarette main flume
Method includes the following steps：
（1）The preparation of CrAPO-5 Primogels：Suspension is made with water in boehmite, later by chromic nitrate water dissolution
Afterwards, it is added in boehmite suspension, is stirred in suspension；Later, it under stirring, is added dropwise
Volumetric concentration is 80~85% phosphoric acid, and after continuing 0.9~1.1h of stirring after adding, three second are added dropwise in the state of stirring
Amine continues 1.9~2.1h of stirring after adding, obtain CrAPO-5 Primogels；
（2）Crystallization, drying and roasting：By step（1）The CrAPO-5 Primogels that prepare are added in reaction kettle, 180~
It at 200 DEG C after 24~48h of crystallization, takes out and is rapidly cooled to room temperature, wash 2 ~ 5 times later, in 118~122 DEG C dry 7.5
~8.5h takes out, and wears into fine powder to 100 mesh, and fine powder finally is roasted 4~6h at 450~650 DEG C, obtains CrAPO-5, can
The modification phosphate aluminium molecular sieve material of hydrocyanic acid release amount in selectivity reducing cigarette main flume.
2. preparation method according to claim 1, which is characterized in that the Al in chromic nitrate, boehmite2O3、H3PO4、
The molar ratio of total dosage of triethylamine and water is n:(1-n):1:0.74~0.76:M, wherein n=0.03~0.09, m=1.00~
1.22。
3. hydrocyanic acid release amount changes in preparation method described in claim 1 energy selectivity reducing cigarette main flume obtained
Property aluminium phosphate molecular sieve material.
4. the modified phosphate aluminum molecular screen of hydrocyanic acid release amount in the energy selectivity reducing cigarette main flume described in claim 3
Material is as the application in cigarette additive.
5. application according to claim 4, which is characterized in that by hydrogen cyanogen in the energy selectivity reducing cigarette main flume
The modified phosphate aluminum molecular screen material of sour burst size is added in cigarette filter.
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| US4195645A (en) * | 1978-03-13 | 1980-04-01 | Celanese Corporation | Tobacco-substitute smoking material |
| CN101195093A (en) * | 2007-12-24 | 2008-06-11 | 上海兖矿能源科技研发有限公司 | Chromium modified silicon aluminum phosphoric acid molecular sieve, preparation method and application thereof |
| CN102205975A (en) * | 2011-05-28 | 2011-10-05 | 山西昆明烟草有限责任公司 | Modified aluminium phosphate molecular sieve additive capable of reducing aldehyde and ketone compound contents in cigarette smoke as well as preparation and application thereof |
| CN107252672A (en) * | 2017-07-21 | 2017-10-17 | 云南中烟工业有限责任公司 | A kind of modified phosphate aluminium molecular sieve filter tip adsorption material and preparation method and application |
| CN107416857A (en) * | 2017-07-21 | 2017-12-01 | 云南中烟工业有限责任公司 | A kind of modified phosphate aluminum molecular screen flue gas sorbing material containing cobalt and preparation method and application |
-
2018
- 2018-01-03 CN CN201810004560.2A patent/CN108187603A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4195645A (en) * | 1978-03-13 | 1980-04-01 | Celanese Corporation | Tobacco-substitute smoking material |
| CN101195093A (en) * | 2007-12-24 | 2008-06-11 | 上海兖矿能源科技研发有限公司 | Chromium modified silicon aluminum phosphoric acid molecular sieve, preparation method and application thereof |
| CN102205975A (en) * | 2011-05-28 | 2011-10-05 | 山西昆明烟草有限责任公司 | Modified aluminium phosphate molecular sieve additive capable of reducing aldehyde and ketone compound contents in cigarette smoke as well as preparation and application thereof |
| CN107252672A (en) * | 2017-07-21 | 2017-10-17 | 云南中烟工业有限责任公司 | A kind of modified phosphate aluminium molecular sieve filter tip adsorption material and preparation method and application |
| CN107416857A (en) * | 2017-07-21 | 2017-12-01 | 云南中烟工业有限责任公司 | A kind of modified phosphate aluminum molecular screen flue gas sorbing material containing cobalt and preparation method and application |
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