CN108246247A - A kind of modified phosphate aluminum molecular screen flue gas sorbing material and preparation method and application - Google Patents
A kind of modified phosphate aluminum molecular screen flue gas sorbing material and preparation method and application Download PDFInfo
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- CN108246247A CN108246247A CN201810004344.8A CN201810004344A CN108246247A CN 108246247 A CN108246247 A CN 108246247A CN 201810004344 A CN201810004344 A CN 201810004344A CN 108246247 A CN108246247 A CN 108246247A
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- flue gas
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- cupric
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000003546 flue gas Substances 0.000 title claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 36
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 30
- 238000004321 preservation Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 229940043279 diisopropylamine Drugs 0.000 claims description 18
- 235000011007 phosphoric acid Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 37
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- -1 aluminium phosphate molecular sieve series Chemical class 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229940001007 aluminium phosphate Drugs 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 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
- 230000000536 complexating effect Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006920 protein precipitation Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000005406 washing Methods 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Modified phosphate aluminum molecular screen flue gas sorbing material the present invention relates to a kind of cupric and preparation method and application, belongs to technical field of cigarettes.The preparation method of the material includes synthesis, crystallization, drying and the calcination steps of 11 Primogels of CuAPO；The modified phosphate aluminum molecular screen flue gas sorbing material of the cupric of well-crystallized is made；Material obtained is added in the middle part of cigarette filter, tests its flue gas adsorption effect, the results showed that, the material its there is good adsorption effect to hydrogen cyanide in flue gas and phenol.Preparation method low raw-material cost of the present invention, crystallization condition is more mild, and low energy consumption.Institute's prepared material protrudes for reducing the hydrogen cyanide that can be effectively reduced after cigarette filter in flue gas and the burst size of phenol, harm reduction effect.
Description
Technical field
Modified phosphate aluminum molecular screen flue gas sorbing material the present invention relates to a kind of cupric and preparation method and application belongs to
In technical field of cigarettes.
Background technology
Smoking is harmful to your health, this is well-known.There are 6000 many kinds of substance to discharge into the atmosphere during cigarette burning, to ring
Border and the mankind can cause serious harm, wherein it is harmful to human body to have more than 500 kinds.For now, it is universally acknowledged
7 kinds of harmful substances just have a great impact to health, such as hydrogen cyanide and phenol.Hydrogen cyanide is a kind of fiber toxin,
Human body respiration can be influenced to cell, when human body takes in a certain amount of hydrogen cyanide, finally because cell asphyxia leads to death；Phenol is
A kind of common fungicide can be absorbed through respiratory tract, skin and alimentary canal, and Low Concentration Phenol can make protein denaturation, high concentration
It can make protein precipitation, there is strong corrosiveness to skin and mucous membrane, also can inhibit central nervous system damage liver kidney function
Can, thus it is very urgent to reduce harmful substance ingredient in cigarette smoke.World tobacco tissue is long to the reducing tar and reducing harm of cigarette
All pay much attention to since phase, the slogan of each member national capital active response reducing tar and reducing harm, while tobacco business is sent out as China's economic
One of pillar industry of exhibition, requirement of the market to cigarette are higher and higher.With do not influence consumer sensory's comfort level and reduce pair
Under the premise of health and social danger, the harmful components in cigarette smoke are reduced, are always the hot spot of tobacco concern.
It is a kind of common method that sorbing material is added in cigarette filter, and at present, the sorbing material added on a large scale in cigarette only has
The porous materials such as activated carbon.
APO-11 molecular sieves are one kind of aluminium phosphate molecular sieve series, after metal heteroatom is mixed, the miscellaneous original that is formed
Sub- molecular sieve has ion-exchange performance, certain acid and excellent thermal stability and hydrothermal stability, while has larger
Specific surface area and regular pore passage structure, therefore get more and more people's extensive concerning, more applying is carried in catalysis, catalyst
Body, ion-exchanger, catalysis, absorption etc..
Porous material is applied individually to any in cigarette filter, has relevant report, but generally, to being harmful into cigarette
The removal effect divided is bad, and selective not strong；In addition the preparation process complexity reported is cumbersome, and production cost is higher.Therefore
How overcome the deficiencies in the prior art, the aluminum phosphate point that research preparation method is simple, good to harmful components selective removal effect
The problem of son sieve is current technical field of cigarettes urgent need to resolve.
Invention content
The purpose of the invention is to improve the deficiencies in the prior art, a kind of modified phosphate aluminum molecular screen cigarette of cupric is provided
Aspiration enclosure material and preparation method and application.The present invention makees the material under the premise of the recipe ingredient of cigarette is not changed
It is made an addition in the middle part of cigarette filter for adsorbent, utilizes the complexing with cyanide ion after material orderly pore passage structure and doping metals
Effect, can selectively reduce the burst size of hydrogen cyanide and phenol in flue gas.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirring 1.5~
2.5h under stirring, is slowly added to copper nitrate aqueous solution, continues 20~40min of stirring after adding, later in the shape of stirring
Under state, diisopropylamine is added dropwise, continues 1.5~2.5h of stirring after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:79~81,
Wherein x+y=1, x=0.02~0.1；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；For the aqueous amount of amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution,
The aqueous amount of copper nitrate aqueous solution is not specifically limited, as long as total amount is in the range of restriction；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 180~200 DEG C after 24~48h of crystallization, cooled to room temperature is washed with water 2~3 times, puts later
Dry 5~8h, takes out, is ground into fine powder of the grain size between 80~110 mesh, finally fine powder exists in 80~120 DEG C of baking ovens
Muffle kiln roasting obtains the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric；
Calcination procedure is that temperature is risen to 200 DEG C of 0 ~ 2h of heat preservation by the heating rate of 3 ~ 5 DEG C/min, then presses 1 ~ 5 DEG C/min again
Heating rate by temperature rise to 350 DEG C heat preservation 1 ~ 3h, temperature is then risen to 550 DEG C by the heating rate of 3 ~ 5 DEG C/min again
Keep the temperature 1~4h.
Preferably, water is to steam used by preparation positive acid solution, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution
Distilled water.
Preferably, step（2）During middle washing, adopt and be washed with deionized.
Preferably, step（2）In, when wearing into fine powder, using agate mortar.
The present invention also provides the modified phosphate aluminum molecular screen flue gas sorbing materials of cupric made from above-mentioned preparation method.
The present invention also provides the modified phosphate aluminum molecular screen flue gas sorbing material conducts of cupric made from above-mentioned preparation method
The application of cigarette additive.
Preferably, the modified phosphate aluminum molecular screen flue gas sorbing material of cupric is added in cigarette filter.
Preferably, addition is 20mg/ branch.
The CuAPO-11 molecular sieves and raw material APO-11 molecular sieves of preparation as stated above are tested through XRD, spectrogram
As shown in Figure 1.The CuAPO-11 molecular sieves synthesized after containing transition metal copper, 2 be located at 9.56 °, 12.74 °, 16.22 °,
21.21 °, 22.49 °, 23.31 ° there is apparent diffraction maximum, while this 6 characteristic peaks correspond to respectively（020）、（200）、
（220）、（002）、（301）、（022）Crystal face, and CuAPO-11 molecular sieves towards（002）Crystal face is grown.It is possible thereby to it determines
The present invention synthesizes the CuAPO-11 molecular screen materials with AEL topological structures.
XPS tests are carried out to CuAPO-11 molecular sieves, curve obtained is as shown in Figure 2.CuAPO-11 molecular sieves are used
XPSPEAK is fitted, and in Cu2p3/2XPS collection of illustrative plates, fitting peak is low at the Cu2p3/2 and 942.8eV at 934.1eV
The satellites that intensity has been shaken, through consulting XPS element databases it is found that the copper at 934.1eV is with existing for divalent state, and is tied
The weaker fitting peak closed at energy 942.8eV is cupric important feature satellite peak.Copper is mixed by can be inferred that above
It is miscellaneous enter after in APO-11 skeletons mainly with existing for divalent state, this effectively improves the neutral bone of APO-11 molecular sieves
Frame structure produces more acidic site, is conducive to the absorption to harmful substances from flue gases.
N is carried out to CuAPO-11 molecular sieves2Physical absorption is tested, gained adsorption-desorption curve and graph of pore diameter distribution such as Fig. 3
It is shown.Adsorption isothermal curve is not be overlapped with desorption curve as can be seen from Figure, shows that, containing mesopore orbit, hysteresis loop belongs to H3
Type, it is tablet narrow slit structure, crack or wedge structure to show mesopore orbit, and this structure is conducive to the part in cigarette smoke
Harmful substance is trapped in the duct of material, has preferable effect for reducing harmful substance.The BET ratios of CuAPO-11 molecular sieves
Surface area is as shown in table 1：
The BET specific surface area of 1 CuAPO-11 molecular sieves of table
As can be seen from the above data, after copper doping is entered, the specific surface area of CuAPO-11 and pure APO-11 molecules
Sieve is substantially little compared to changing, and the Kong Rong that the material is calculated by BJH methods is 0.31cm3/ g, average pore size 5.71nm.
Aluminium phosphate molecular sieve is known as third generation molecular sieve, is because the skeleton structure of its molecular sieve is by phosphorus oxygen tetrahedron
The positive tetrahedron structure strictly alternately formed with aluminum-oxygen tetrahedron, is easily replaced the phosphorus or oxygen in skeleton by other hetero atoms,
Phosphorus or aluminium therein are replaced with transition metal Cu herein, form the new tetrahedral framework with strong acidity position, this is novel
Structure feature can have the ingredients such as hydrogen cyanide in flue gas stronger suction-operated, effectively reduce the release of harmful substances in flue gas
Amount.And the APO-11 selected by the present invention is as a member of aluminium phosphate molecular sieve family that not only synthetic method is relatively simple easy to operate same
When all characteristics with aluminium phosphate molecular sieve.
Compared with prior art, the present invention advantage is：
（1）Copper nitrate is proportionally doped in APO-11 system with molecular sieve for preparing for during by the present invention, makes APO-11 points of Cu substitutions
Phosphorus oxygen tetrahedron and phosphorus or aluminium in aluminum-oxygen tetrahedron skeleton in son sieve, form the new tetrahedron with strong acidity site
Skeleton has the smoke components such as hydrogen cyanide and phenol preferable selection suction-operated；
（2）The present invention prepares CuAPO-11 molecular screen primary powders using hydrothermal synthesis method, and changing for cupric is obtained by high-temperature roasting
Property aluminium phosphate molecular sieve flue gas sorbing material.Through X-ray powder diffraction, X ray electron spectrometer analysis, nitrogen physisorption and
Cigarette adds experiment test, the results showed that the APO-11 molecular sieves of doping metals Cu have the topology of the AEL of APO-11 molecular sieves
Structure, compared to pure APO-11 molecular sieves, it is substantially little that the specific surface areas of CuAPO-11 molecular sieves, aperture and hole hold variation.This
Invention uses copper nitrate to be easily removed for source of metal atoms compared to anhydrous cupric sulfate impurity, is easy to replace APO-11 molecular sieves
Al or P in skeleton form the novel acid material with ion-exchange performance and centainly of cupric；Compared to 200
DEG C or more crystallization temperature, crystallization temperature of the present invention is more mild at 180 ~ 200 DEG C, the crystallization time compared to 72h, the present invention
For crystallization time in 24 ~ 48h, energy consumption is relatively low；The present invention is using temperature-programmed calcination, at different temperature selective removing
The impurity such as water, template obtain the good CuAPO-11 molecular sieves of crystallization degree；
（3）By the addition manner of cigarette filter granular materials normally, changing for 20mg/ branch cuprics is added in cigarette filter
Property aluminium phosphate molecular sieve flue gas sorbing material after, detect its harmful ingredients in flue gas variation, find the material to hydrogen cyanide and phenol
It waits ingredients that there is stronger adsorption capacity, suction-operated is especially had good selectivity to hydrogen cyanide, and migrate and examine through material
It surveys, determines that material will not migrate in itself with flue gas, there is good safety.The sorbing material is used as cigarette filter-tip additive agent
Advantage be：Low raw-material cost, synthesis crystallization condition is more mild, and low energy consumption；Institute's prepared material of the present invention is filtered for cigarette
After mouth, the burst size of the hydrogen cyanide and phenol in flue gas can be effectively reduced.It has been reported that using titanate nanometer sheet as additive,
In the case that additive amount is 20mg/ branch, reduction HCN distinguishes 22.9% with phenol and is compared with 49.1%, the addition of CuAPO-11 molecular sieves
20mg/ branch is measured, highest can reduce HCN45.56% and phenol 33.66%；With the functionalized polyethy-lene imines having been reported that, the choosing of HCN
Selecting property reduced rate is up to 72.1%, but Sensory Quality of Cigarette has certain reduction, CuAPO-11 molecular sieve additive amount 20mg/ branch, HCN
Highest can reduce by 41.25%, and phenol reduced rate is 38.03%, while other compositions in flue gas be influenced little.
Description of the drawings
Fig. 1 is the XRD spectra of sample after the roasting of APO-11 and CuAPO-11 molecular sieves.
Fig. 2 is the XPS collection of illustrative plates of CuAPO-11 molecular sieves
Fig. 3 is physical absorption-desorption curve of CuAPO-11 molecular sieves.
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
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 1.5h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 20min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 1.5h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:79, wherein
X+y=1, x=0.02；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 180 DEG C crystallization for 24 hours after, cooled to room temperature adopts be washed with deionized 3 times later, is placed in
Dry 5h, takes out, fine powder of the grain size between 80~110 mesh is ground into using agate mortar, finally by fine powder in 110 DEG C of baking ovens
In Muffle kiln roasting, the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric is obtained；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 0h, then the liter by 1 DEG C/min by the heating rate of 5 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 1h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 4h by the heating rate of 5 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Embodiment 2
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 2.5h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 40min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 2.5h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:81,
Middle x+y=1, x=0.02；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 200 DEG C after crystallization 48h, cooled to room temperature adopts be washed with deionized 2 times later, is placed in 80
Dry 5h, takes out, is ground into fine powder of the grain size between 80~110 mesh using agate mortar, finally fine powder exists in DEG C baking oven
Muffle kiln roasting obtains the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 2h, then the liter by 5 DEG C/min by the heating rate of 3 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 3h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 1h by the heating rate of 3 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Embodiment 3
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 2.0h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 30min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 2.0h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:81, wherein
X+y=1, x=0.07；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 190 DEG C after crystallization 36h, cooled to room temperature adopts be washed with deionized 3 times later, is placed in
Dry 7h, takes out, fine powder of the grain size between 80~110 mesh is ground into using agate mortar, finally by fine powder in 110 DEG C of baking ovens
In Muffle kiln roasting, the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric is obtained；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 0h, then the liter by 2 DEG C/min by the heating rate of 3 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 2h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 3h by the heating rate of 3 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Embodiment 4
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 1.7h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 25min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 1.7h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:80, wherein
X+y=1, x=0.03；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 185 DEG C after crystallization 30h, cooled to room temperature adopts be washed with deionized 2 times later, is placed in 90
Dry 7h, takes out, is ground into fine powder of the grain size between 80~110 mesh using agate mortar, finally fine powder exists in DEG C baking oven
Muffle kiln roasting obtains the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 0h, then the liter by 3 DEG C/min by the heating rate of 4 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 2h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 2h by the heating rate of 4 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Embodiment 5
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 2.3h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 35min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 2.3h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:80,
Middle x+y=1, x=0.1；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 195 DEG C after crystallization 42h, cooled to room temperature adopts be washed with deionized 3 times later, is placed in
Dry 5h, takes out, fine powder of the grain size between 80~110 mesh is ground into using agate mortar, finally by fine powder in 120 DEG C of baking ovens
In Muffle kiln roasting, the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric is obtained；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 0h, then the liter by 4 DEG C/min by the heating rate of 5 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 3h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 4h by the heating rate of 5 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Embodiment 6
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 1.9h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 35min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 2.3h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:79, wherein
X+y=1, x=0.08；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 193 DEG C after crystallization 38h, cooled to room temperature adopts be washed with deionized 2 times later, is placed in
Dry 6h, takes out, fine powder of the grain size between 80~110 mesh is ground into using agate mortar, finally by fine powder in 100 DEG C of baking ovens
In Muffle kiln roasting, the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric is obtained；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 0h, then the liter by 3 DEG C/min by the heating rate of 5 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 2h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 2h by the heating rate of 5 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Embodiment 7
A kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirs 2.5h,
Under stirring, copper nitrate aqueous solution is slowly added to, continues to stir 35min after adding, later in the state of stirring, is added dropwise
Enter diisopropylamine, continue to stir 1.7h after adding to get to CuAPO-11 Primogels；
Wherein, the molar ratio of total dosage of copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine and water is x:y:1:1:80, wherein
X+y=1, x=0.05；
The amount and nitric acid that total dosage of the water is amount aqueous in positive acid solution, aluminium isopropoxide aqueous solution is aqueous
The sum of aqueous amount of copper liquor；
（2）Crystallization, drying and roasting：By step（1）It is interior that the CuAPO-11 Primogels prepared, which are added in using polytetrafluoroethylene (PTFE),
In the reaction kettle of lining, at 200 DEG C after crystallization 27h, cooled to room temperature adopts be washed with deionized 3 times later, is placed in
Dry 8h, takes out, fine powder of the grain size between 80~110 mesh is ground into using agate mortar, finally by fine powder in 110 DEG C of baking ovens
In Muffle kiln roasting, the modified phosphate aluminum molecular screen flue gas sorbing material of CuAPO-11 molecular sieves, i.e. cupric is obtained；
The calcination procedure is that temperature is risen to 200 DEG C of heat preservation 0h, then the liter by 4 DEG C/min by the heating rate of 5 DEG C/min
Temperature is risen to 350 DEG C of heat preservation 2h by warm rate, and temperature then is risen to 550 DEG C of heat preservation 4h by the heating rate of 5 DEG C/min again.
Wherein, water is distilled water used by preparation orthophosphoric acid water, aluminium isopropoxide aqueous solution and copper nitrate aqueous solution.
Application process
Sorbing material prepared by embodiment 1 to 7 is made an addition to by 20mg/ branch in the middle part of cigarette filter, using blank cigarette as control
Group is in temperature（22±2）DEG C, humidity is（66±2）%, under conditions of balance 48h, finally in German Borgwaldt companies
Absorption test is carried out on SM450 linear type smoking machines.The measure of flue gas correlation component content is carried out with reference to industry standard methods.
The use of cigarette is conventional cigarette that formal production line produces.It the results are shown in Table 2.
Table 2
It, can be preferably after upper table testing result can be seen that the sorbing material added in cigarette filter prepared by the present invention
Reduce flue gas in the burst size of HCN and phenol.
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of preparation method of the modified phosphate aluminum molecular screen flue gas sorbing material of cupric, includes the following steps：
（1）The preparation of CuAPO-11 Primogels：Positive acid solution is added in aluminium isopropoxide aqueous solution, stirring 1.5~
2.5h under stirring, is slowly added to copper nitrate aqueous solution, continues 20~40min of stirring after adding, later in the shape of stirring
Under state, diisopropylamine is added dropwise, continues 1.5~2.5h of stirring after adding to get to CuAPO-11 Primogels；
（2）Crystallization, drying and roasting：By step（1）The CuAPO-11 Primogels that prepare are added in reaction kettle, 180~
At 200 DEG C after 24~48h of crystallization, cooled to room temperature is washed with water 2~3 times later, in 80~120 DEG C of dry 5~8h,
It takes out, is ground into fine powder of the grain size between 80~110 mesh, finally by fine powder in Muffle kiln roasting, obtain CuAPO-11 points
Son sieve, i.e. the modified phosphate aluminum molecular screen flue gas sorbing material of cupric.
2. preparation method according to claim 1, which is characterized in that copper nitrate, aluminium isopropoxide, orthophosphoric acid, diisopropylamine
Molar ratio with total dosage of water is x:y:1:1:79~81, wherein x+y=1, x=0.02~0.1.
3. preparation method according to claim 1, which is characterized in that step（2）Middle calcination steps are by 3 ~ 5 DEG C/min's
Temperature is risen to 200 DEG C of 0 ~ 2h of heat preservation by heating rate, and temperature then is risen to 350 DEG C of guarantors by the heating rate of 1 ~ 5 DEG C/min again
Then temperature is risen to 550 DEG C of 1~4h of heat preservation by 1 ~ 3h of temperature by the heating rate of 3 ~ 5 DEG C/min again.
4. preparation method according to claim 1, which is characterized in that prepare positive acid solution, aluminium isopropoxide aqueous solution
It is distilled water with water used by copper nitrate aqueous solution.
5. the modified phosphate aluminum molecular screen flue gas absorption of cupric made from the preparation method in claim 1-4 described in any one
Material.
6. application of the modified phosphate aluminum molecular screen flue gas sorbing material of the cupric described in claim 5 as cigarette additive.
7. application according to claim 6, which is characterized in that by the modified phosphate aluminum molecular screen flue gas sorbing material of cupric
It is added in cigarette filter.
8. application according to claim 7, which is characterized in that addition is 20mg/ branch.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4195645A (en) * | 1978-03-13 | 1980-04-01 | Celanese Corporation | Tobacco-substitute smoking material |
| CN1351960A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Aluminium silkicon phosphate molecular sieve and its preparing method |
| 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 CN201810004344.8A patent/CN108246247A/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 |
| CN1351960A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Aluminium silkicon phosphate molecular sieve and its preparing method |
| 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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