CN107724180A - A kind of preparation method with combustion-supporting and drop CO discharge capacity functions cigarette paper - Google Patents
A kind of preparation method with combustion-supporting and drop CO discharge capacity functions cigarette paper Download PDFInfo
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- CN107724180A CN107724180A CN201610657249.9A CN201610657249A CN107724180A CN 107724180 A CN107724180 A CN 107724180A CN 201610657249 A CN201610657249 A CN 201610657249A CN 107724180 A CN107724180 A CN 107724180A
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- pulp
- cigarette paper
- acid
- dispersion liquid
- cellulose
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
Abstract
The present invention relates to a kind of with combustion-supporting and reduction CO discharge capacity functions cigarette paper preparation method.The preparation method comprises the following steps：Pure plant nanofiber combustion adjuvant (functionalized nano-fiber) is prepared by chemical method and high-pressure homogeneous Combined Treatment cellulosic material, then obtained nanofiber combustion adjuvant is mixed with the slurry for cigarette paper of manufacturing paper with pulp, or the combustion-supporting agent dispersing liquid surface coating/top sizing of nanofiber is prepared into the cigarette paper that nanofiber combustion adjuvant is modified in commodity cigarette paper surface.The cigarette paper being modified by the pure plant nanofiber combustion adjuvant of the present invention has good combustion-supporting and drop CO discharge capacity functions, the cigarette paper smoldering velocity of preparation is fast compared with regular-size cigarette paper, CO discharge capacitys significantly reduce, and grey is in canescence after burning, outward appearance is preferable, available for production high quality cigarette, and the injury to health can be reduced.
Description
Technical field
The present invention relates to field of special paper production, in particular to a kind of with combustion-supporting and reduction CO discharge capacity functions
Cigarette paper preparation method.
Background technology
In recent years, people pay high attention to influence of the smoking to health, improve the security of smoking and have turned into whole world pass
The problem of note.Cigarette includes pipe tobacco and cigarette paper, and its combustion high temperature area temperature is about in 700-900 DEG C of (Carbohydrate
Polymers,2014,101,769-775).It is anti-that cigarette such as can aoxidize, be pyrolyzed, polymerizeing at a series of chemistry in combustion
Should, the imperfect combustion of its organic principle and destructive distillation can form tar and some other harmful substance (such as CO)
(BioResources,2013,8,1517-1519).Therefore, the composition of cigarette smoke and the content not only chemistry with tobacco in itself
Form it is closely related, it is also closely coupled with the fired state of cigarette.So except to tobacco leaf compositing formula, cigarette producing process,
Reconstituted tobacoo addition etc. is improved outside pipe tobacco performance, also needs to be improved the combustibility of cigarette paper.
Improving the method for cigarette paper combustibility mainly includes two aspects：
1) to the control of air permeance for cigarette paper.Existing document report (paper and papermaking, 2008,27 (4), 33-36), cigarette paper
Air permeability has a major impact to reducing harmful components, puff number, smoke's total particulate matter, nicotine and the CO content meetings of cigarette
Reduced with the increase of cigarette paper natural permeable degree, but when cigarette paper natural permeable degree is more than 70CU, air permeability not only can not
Tar content is reduced, but also the suction taste (spectrographic laboratory, 2009,26 (6), 1464-1468) of cigarette can be influenceed.It can lead to
Cross using rational raw material proportioning and improve beating process to control the air permeability of cigarette paper.In addition, the use of filler can also
Improve the air permeability of cigarette paper.For example, addition of the precipitated calcium carbonate in cigarette paper can reach more than 40%.In document
In (papermaking chemical product, 2007,19 (3), 40-45), Wang Ying have studied calcium carbonate dosage, different sources calcium carbonate and different cultivars
Influence of the calcium carbonate to cigarette paper, cigarette's quality.With going deep into for research, people start to replace part carbonic acid with filler auxiliary agent
Calcium.For example, in document (paper and papermaking, 2008,27 (4), 33-36), the report such as Xie Lanying, British American Tobacco is in cigarette paper
Add the hydroxide and potassium formate of a kind of lithium, aluminium or calcium, Reynolds scholar company of the U.S. added in cigarette paper inorganic mineral and
The compositions such as carboxylate, 50% flow measurement flue gas can be reduced, reduce the pollution to surrounding environment, and cigarette paper opacity, thoroughly
Manner and ash content have different degrees of improvement, but this environment-friendly type cigarette paper is quantitatively higher, and the suction taste to cigarette has certain
Influence.
2) harmful ingredients in flue gas is reduced by adding cigarette paper auxiliary agent, adjuvant used mainly combustion adjuvant, also included few
Measure ash conditioners and fire retardant.Combustion adjuvant can improve the burning velocity of cigarette paper, puff number be reduced, so as to reduce cigarette
Harm, while combustion adjuvant can also reach the purpose of reduction tar content by reducing the ignition temperature during aspirating.It is conventional at present
Combustion adjuvant have the citrate of alkali metal, nitrate, tartrate, chloride etc., the change of its species and dosage can influence
The smoldering velocity and ventilation rate of cigarette paper, so as to influence the suction taste of cigarette and exhaust gas volumn.Document (zur
Tabakforschung International, 1990,14,379-385) in, the report such as Yamatomo, added in cigarette paper
After potassium malate and potassium nitrate, ignition temperature, tar content, nicotine content, the CO contents of cigarette all decrease.Document (China
Papermaking, 2007,26 (7), 8-12) in Hou Yi et al. have studied Mg (OH) is added in cigarette paper2Influence to cigarette smoke, knot
Fruit finds the Mg (OH) of content 8%2Preferable to reducing cigarette smoke effect, TPM amount, nicotine, tar and CO contain in flue gas
Amount have dropped 6.0%, 6.6%, 5.5% and 8.6% respectively.Filler can be pyrolyzed by being reported in United States Patent (USP) US6817365
Particle is (by alkylcellulose, ethyl cellulose, the esters cellulose of mixing and mono phosphoric acid ester sodium, disodium hydrogen phosphate, polycyclic oxygen second
Alkane, vinylacetate, polymethacrylates, nitrocellulose or its mixture composition) it is added in cigarette paper cigarette is made, can
To control and reduce cigarette burning temperature, nuisance total amount caused by cigarette burning is reduced.Can be complete in addition, being added in cigarette paper
The carbohydrate to burn entirely, the moisture of the TPM of cigarette combustion can be increased, and tar content can relative reduction.Added in cigarette paper
Adsorbent or catalyst can the harmful substances such as the tar adsorption of selectivity, CO, heavy metal.Chinese invention patent
Reported in 200610010787.5, several organic acid salt of multihydroxyl of single organic acid salt of multihydroxyl or any combination are mixed
Thing is added to tobacco leaf, expanded cut tobacco, stem, reconstituted tobacoo or cigarette paper by the addition for the 0.2-5% for accounting for cigarette materials dry weight
In, the content of CO and tar in cigarette mainstream flue gas can be reduced.Report, rolling up in Chinese invention patent 201310080145.2
Metal oxide, citric acid, hydrogen malate potassium, the potassium citrate of more dimeric molecule encapsulated water, vulcanized sodium, magnesium and cerium are added in cigarette paper
One or more in salt and magnesium salts mix in proportion, addition 0.1-0.9%, cigarette paper can be made to have drop CO and humectation work(
Energy.But the above-mentioned cigarette paper obtained in the prior art still has that such as CO discharge capacitys are higher, and ashes are faint in color after burning
Problem.
In summary, the focus that green, economical and effective cigarette paper combustion adjuvant is still cigarette paper development field is developed to ask
Topic.
The content of the invention
It is an object of the invention to provide one kind to have combustion-supporting and drop CO discharge capacity functions, and more abundant, the ashes color that burns
Ze Gengbai cigarette paper preparation method.
To achieve the above object, preparation in accordance with the present invention comprises the following steps：
1) cellulosic material is utilized, passes through the mineral acid hydrolysis of high concentration, organic acid hydrolysis, solid acid hydrolysis, periodic acid
After salt oxidation, TEMPO oxidations or carboxy methylation processing, optionally carry out high-pressure homogeneous processing and pure plant nano combustion improver is made
(functionalized nano-fiber) dispersion liquid.The functionalized nano-fiber, its diameter are about 1-100nm, and length can arrive for 10nm
Several microns, can be cellulose nano microcrystalline (cellulose nanocrystals), cellulose nanometer fibril (cellulose
Nanofibrils one kind) or its mixing.
2) it is 0.01%-2% obtained pure plant nano combustion improver dispersion liquid in step 1) to be diluted into mass concentration, excellent
Elect 0.5%-1% as.
3) the pure plant nano combustion improver dispersion liquid prepared in step 2) is added to match somebody with somebody and manufactured paper with pulp in the slurry for copying cigarette paper
Cigarette paper, the dosage of pure plant nano combustion improver are 0.01%-8%, the preferably 1-3% of over dry stock quality, after drying i.e.
The cigarette paper being modified through pure plant nano combustion improver is made.
4) alternatively, the pure plant nano combustion improver dispersion liquid prepared in step 2) is directly coated with or top sizing
To cigarette paper into paper surface, the cigarette paper being modified through pure plant nano combustion improver can be made after drying.Pure plant nano combustion improver
Coating weight remain the pure plant nano combustion improver of every square metre of cigarette paper coating and be maintained at 0.005-2g, i.e. 0.005-2g/
m2, preferably 0.1-1.0g/m2, more preferably 0.4-0.6g/m2, the matter of described pure plant nano combustion improver dispersion liquid
Amount concentration is 0.01%-2%, preferably 0.5%-1%.
Preferably, inorganic acid described in the step 1) is selected from sulfuric acid, nitric acid and hydrochloric acid, preferably sulfuric acid；The solid
Acid is selected from phosphotungstic acid, silica-rich zeolite (ZSM-5), cationic ion-exchange resin etc., preferably phosphotungstic acid；The organic acid has to be polynary
Machine acid, preferably malic acid, tartaric acid or citric acid.
Preferably, in preparation method according to the present invention, other auxiliary agents, such as catalyst etc. are not used.
Preferably, in step 1), for example, the preparation method of the pure plant nano combustion improver dispersion liquid can select such as
It is one of lower：
(1) sulphuric acid hydrolysis
Take the sulfuric acid that the mass concentration of the cellulosic material addition 10-50 parts by weight of 1 parts by weight is 35wt%-72wt% molten
Liquid reacts 0.5-2 hours in 35-65 DEG C.After reaction terminates, mixed solution is placed in fast cooling in ice bath, and pass through centrifugation
Mode fully washs the cellulosic material of sulphuric acid hydrolysis, and it is constant to pH value to be then placed on dialysis in bag filter.The fibre
Tie up plain raw material and be selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose.
(2) hydrochloric acid hydrolysis+high-pressure homogeneous processing
Take the hydrochloric acid that the mass concentration of the cellulosic material addition 10-45 parts by weight of 1 parts by weight is 36wt%-38wt% molten
Liquid reacts 1-6 hours in 70-100 DEG C.Reaction is former by the cellulose after HCl treatment by way of centrifuging or filtering after terminating
Material is cleaned, and the cellulose dispersion liquid for 0.1wt%-0.9wt% is diluted with water, and the dispersion liquid then is carried out into high-pressure homogeneous place
Reason, homogeneous 3-30 times, preferably 45MPa-95MPa under 25MPa-120MPa pressure, homogenization cycles are preferably 6-12 times.Institute
State cellulosic material and be selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose.
(3) malic acid hydrolysis+high-pressure homogeneous processing
The cellulosic material of 1 parts by weight is taken, the mass concentration for adding 15-50 parts by weight is 60wt%-90wt% apple
Acid solution reacts 4-16 hours in 80-140 DEG C, reacts the fibre after malic acid is hydrolyzed by way of centrifuging or filtering after terminating
Tie up plain raw material to clean, and the cellulose dispersion liquid for 0.1wt%-0.9wt% is diluted with water, the dispersion liquid is then entered into horizontal high voltage
Homogenization, homogeneous 3-20 times, preferably 45MPa-60MPa under 25MPa-100MPa pressure, homogenization cycles are preferably 5-8
It is secondary.It is fine that the cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or crystallite
Dimension element.
(4) tartaric acid hydrolysis+high-pressure homogeneous processing
The cellulosic material of 1 parts by weight is taken, the mass concentration for adding 15-55 parts by weight is 60wt%-90wt% winestone
Acid solution reacts 4-12 hours in 90-140 DEG C, reacts the fibre after malic acid is hydrolyzed by way of centrifuging or filtering after terminating
Tie up plain raw material to clean, and the cellulose dispersion liquid for 0.1wt%-0.9wt% is diluted with water, the dispersion liquid is then entered into horizontal high voltage
Homogenization, homogeneous 3-20 times, preferably 45MPa-60MPa under 25MPa-100MPa pressure, homogenization cycles are preferably 5-8
It is secondary.It is fine that the cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or crystallite
Dimension element.
(5) citric acid hydrolysis+high-pressure homogeneous processing
The cellulosic material of 1 parts by weight is taken, the mass concentration for adding 10-55 parts by weight is 30wt%-90% citric acid
Solution in 85-140 DEG C react 4-12 hours, reaction terminate after by way of centrifuging or filtering by the cellulosic material after hydrolysis
Clean, take upper strata suspension directly to use after can standing.Also dilutable water is that 0.1wt%-0.9wt% cellulose disperses
Liquid, the dispersion liquid is then subjected to high-pressure homogeneous processing, homogeneous 3-35 times under 25MPa-120MPa pressure, is preferably
45MPa-95MPa, homogenization cycles are preferably 6-12 times.The cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, fiber crops
Slurry, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose.
According to another aspect of the present invention, it is an object of the present invention to provide a kind of cigarette paper, the cigarette paper
It is prepared by above-mentioned preparation in accordance with the present invention.
Beneficial effect
It is 1. of the invention mainly using pure plant nano combustion improver dispersion liquid by the way of addition in slurry or surface coating
Cigarette paper is modified, prepared with combustion-supporting and drop CO discharge capacity functions cigarette paper, pure plant nano combustion improver used
From pure natural plant fiber, there is green, sustainability and reproducible advantage.
2. cigarette paper smoldering velocity prepared by the present invention is fast compared with regular-size cigarette paper, CO discharge capacitys significantly reduce, and after burning
Grey is in canescence, and outward appearance is preferable, available for production high quality cigarette, and can reduce the injury to health.
Brief description of the drawings
Fig. 1 is according to after the cigarette paper that with the addition of plant nanometer combustion adjuvant of the preparation of embodiment 1 and the burning of blank cigarette paper
Residual grey comparison diagram；
Fig. 2 is that with the addition of the cigarette paper of plant nanometer combustion adjuvant and the thermogravimetric matter of blank cigarette paper according to prepared by embodiment 1
Spectrum combination test result figure；
Fig. 3 is that the nanofiber prepared according to blank cigarette paper prepared by traditional handsheet method with addition according to embodiment 3 helps
Fire the SEM photograph comparison diagram of the cigarette paper of agent；
Embodiment
Hereinafter, it will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of appropriate definition term is to carry out the principle of best interpretations, according to implication corresponding with the technical elements of the present invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The scope of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
Pure plant nano combustion improver used in the present invention is the nano-cellulose of functionalization, due to itself heat endurance compared with
It is low, in the cigarette paper that a small amount of nano-cellulose is added, the burning of cigarette paper can be promoted, and it is more fully burnt,
So that the ashes after burning are in canescence, CO discharge capacitys reduce.
In the step 3) of preparation in accordance with the present invention, the pure plant nano combustion improver prepared in step 2) is disperseed
Liquid is added to cigarette paper of being manufactured paper with pulp in the slurry for copying cigarette paper, and the dosage of pure plant nano combustion improver is over dry stock quality
0.01%-8%, preferably 1-3%.If dosage is too low to cause DeGrain, if dosage can excessively cause nanofiber to help
Firing agent retention reduces, and manufactured cigarette paper air penetrability is too low, influences burning, the increase of CO discharge capacitys on the contrary.This be probably because,
If dosage is excessive, negative electrical charge is excessive in slurry, and nano combustion improver can be caused to be not easy to keep on paper pulp, although keeping on paper pulp
Nano combustion improver it is fewer than dosage when it is more, but understand some loss, cause corresponding retention to reduce.
In the step 4) of preparation in accordance with the present invention, the pure plant nano combustion improver prepared in step 2) is disperseed
Liquid is directly coated with or top sizing is to cigarette paper into paper surface, and the cigarette being modified through pure plant nano combustion improver can be made after drying
Paper.The mass concentration of described pure plant nano combustion improver dispersion liquid is 0.01%-2%, preferably 0.5%-1%.If its is dense
Spend it is low can cause DeGrain, if its excessive concentration can cause, air permeance for cigarette paper is too low, and smoldering velocity is excessively slow, CO discharge
Amount increases on the contrary.
Prepared functionalized nano-fiber diameter is smaller, size distribution is more uniform, surface functional group is more, its combustion-supporting effect
Fruit is better, and function base substitutes more uniform application effect better.The content of the combustion adjuvant surface functional group is relevant with reaction condition,
Such as acid concentration is reacted, reaction time and temperature etc.；Reaction is more abundant, and functional group content is higher, and combustion-supporting effect is accordingly
Better；In addition, combustion adjuvant particle diameter is smaller, size distribution is more uniform, and combustion-supporting effect is also better；It should be understood that combustion adjuvant
The content of surface functional group might not be smaller corresponding with particle diameter.The content of combustion adjuvant surface functional group should be greater than 0.1%, if
Its size distribution is uneven, or the substitution of its surface functional group is uneven, then its combustion-supporting effect can be unstable.It is of the present invention
Pure plant nano combustion improver can not only obtain combustion-supporting effect, it might even be possible to as fire retardant in the case of using excess
Use.
Following examples are laboratory scale experiments, are enumerated only as the example of embodiment of the present invention, not right
The present invention forms any restrictions, it will be appreciated by those skilled in the art that in the range of without departing from the essence of the present invention and design
Change or be expanded to plant production scale and each fall within protection scope of the present invention.
Embodiment 1
1g bleaching needle-point leaf pulps are taken to be added in the 50mL 64wt% concentrated sulfuric acids, 45 DEG C are reacted 1 hour.After reaction terminates,
Reaction vessel is put into terminating reaction in ice bath, mixed liquor then is moved into centrifuge tube is centrifuged under 8000rpm with deionized water
5min is washed 6 times repeatedly, then removes residual acid with dialysis, pure plant nano combustion improver is just made after pH value is constant, then
It is configured to 0.6wt% dispersion liquid.One side coating is carried out on coating machine with the dispersion liquid prepared into paper to cigarette paper (to apply
Cloth amount is 0.4g/m2), vacuum drying afterwards obtains modified cigarette paper products.The cigarette paper prepared by method in this example
Intensity increases to 1.21kN/m by the 1.09kN/m of blank sample, and 10cm smoldering velocities are reduced to 49.35s by 61.25s, treated
Sample strength increase, burn rate substantially accelerate.The functional group content of the nano combustion improver is 0.67% (its measuring method use
Document " method of report in ACS Applied Materials＆Interfaces, 2015,7,5006-5016 ").Fig. 1 is root
Residual grey comparison diagram after being burnt according to the cigarette paper manufactured in the present embodiment that with the addition of plant nanometer combustion adjuvant and blank cigarette paper, its
In from burn it is residual ash this it appears that containing pure plant nano combustion improver cigarette paper burning it is more abundant, residual ash is whiter, in Fig. 1
Left figure is blank control commodity cigarette paper, and right figure is the cigarette paper containing nanofiber combustion adjuvant, so in cigarette aspiration procedure
The outward appearance of middle cigarette can be more preferable, available for producing high-grade cigarette.
Embodiment 2
In the citric acid solution for taking the 80wt% that 1g bleached hardwood pulp is added to 75mL, the stirring reaction 3 at 150 DEG C
Hour.After reaction terminates, centrifugal sedimentation 8min under reactant mixture 8000rpm is washed with water 3 times repeatedly, the mixing after washing
Thing further removes water-soluble residue by dialysis.Solidliquid mixture after dialysis is high-pressure homogeneous 10 times through 60Mpa, further
Improve its water slurry stability and nanofiber homogeneity, so as to obtain nanofiber combustion adjuvant, be then made into
0.8wt% dispersion liquid.Into paper carrying out one side coating with the dispersion liquid prepared to cigarette paper on coating machine, (coating weight is
0.5g/m2), vacuum drying afterwards obtains modified cigarette paper products.By in this example method handle cigarette paper intensity by
The 1.08kN/m of blank sample increases to 1.16kN/m, and 10cm smoldering velocities are reduced to 51.35s by 60.15s, and treated sample is strong
Spend bigger, burn rate faster.The nano combustion improver functional group content is that 0.34% (its measuring method uses document
" method of report in Cellulose, 21,2587-2598 ").Fig. 2 is that to the addition of plant nanometer combustion-supporting according to manufactured in the present embodiment
The cigarette paper and blank commodity cigarette paper thermogravimetric mass spectrometry test result figure of agent, wherein thermogravimetric condition：20 DEG C of heating rate/
Min, atmosphere form oxygen/argon=1/5,25-900 DEG C of heating temperature range, and left figure is blank control commodity cigarette in Fig. 2
Paper, right figure are according to the cigarette paper manufactured in the present embodiment containing nanofiber combustion adjuvant.It can be seen that by pure plant nanometer
CO release of the cigarette paper of combustion-supporting agent dispersing liquid coating in heating process significantly reduces, and CO discharge capacitys reduce about 50%.So
Nano-cellulose can effectively reduce the releases of poisonous CO in combustion in cigarette paper.
Embodiment 3
In the malic acid solution for taking the 80wt% that 2g cotton fiber is added to 90mL, stirring reaction 8 hours at 120 DEG C.
After reaction terminates, centrifugal sedimentation 10min under reactant mixture 10000rpm is washed with water 4 times repeatedly, the mixture after washing
Water-soluble residue is further removed by dialysis.Solidliquid mixture after dialysis, which is stood, takes upper strata suspension, or 3000rpm
Centrifugation 5min takes upper strata suspension, and by suspension preparation into the pure plant nano combustion improver dispersion liquid that mass concentration is 1%.So
Obtained pure plant nano combustion improver dispersion liquid and scattered bleaching needle-point leaf pulp are mixed afterwards, using traditional handsheet, vacuum
Cigarette paper (formula is made in drying process：The quantitative 30g/m of copy paper2, reinforcing agent (anion guar gum) 0.7%, retention agent (sun from
Sub- guar gum) 0.07%, calcium carbonate 30%, pure plant nano combustion improver 3%, dosage is based on over dry bleached wood pulp weight).Add
Pure plant nano combustion improver is added obtained cigarette paper tensile strength is brought up to 1.49kN/m, 10cm by the 1.47kN/m of blank sample
Smoldering rate is reduced to 59.70s by 68.25s, and cigarette paper can be made by starching the nanofiber handsheet that the interior a small amount of little particle of addition suspends
Intensity slightly improve, but Smoldering rate is improved significantly.The nano combustion improver functional group content is 0.42% (its measurement side
Method using document " method of report in Cellulose, 21,2587-2598 ").Accompanying drawing 3 is to be prepared according to above-mentioned traditional handsheet method
Blank cigarette paper and addition according to the SEM photograph comparison diagram of the cigarette paper of nanofiber combustion adjuvant manufactured in the present embodiment, can
Many nanofibers are distributed with the cigarette paper surface for being clearly visible addition nanofiber combustion adjuvant.
Embodiment 4
Take 2g bamboo pulp to dissolve in the tartaric acid solution for the 75wt% that pulp fibres are added to 100mL, stirred at 130 DEG C anti-
Answer 6 hours.After reaction terminates, centrifugal sedimentation 10min under reactant mixture 10000rpm is washed with water 6 times, after washing repeatedly
Mixture by dialysis further remove water-soluble residue.Solidliquid mixture after dialysis, which is stood, takes upper strata suspension, or
Person 3000rpm centrifugations 5min takes upper strata suspension, and suspension preparation is disperseed into the pure plant nano combustion improver that concentration is 1%
Liquid.Then two-sided applying glue (resin added 0.6g/m is carried out with the dispersion liquid prepared into paper to cigarette paper on coating machine2), vacuum
It is dried to obtain modified cigarette paper products.Cigarette paper intensity increases to 1.12kN/m by the 1.09kN/m of blank sample in this example,
10cm smoldering velocities are reduced to 53.35s by 61.25s, and CO discharge capacitys reduce by 47%.The nano combustion improver functional group content is
0.51% (its measuring method using document " method of report in Cellulose, 21,2587-2598 ").
Comparative example 1
1g bleaching needle-point leaf pulps are taken to be added in the 50mL64wt% concentrated sulfuric acids, 45 DEG C are reacted 1 hour., will after reaction terminates
Reaction vessel is put into terminating reaction in ice bath, and mixed liquor then is moved into centrifuge tube is centrifuged under 8000rpm with deionized water
5min is washed 6 times repeatedly, finally removes residual acid using dialysis, nanofiber combustion adjuvant is just made after pH value is constant, so
The overrich dispersion liquid that mass concentration is 2.2wt% is configured to afterwards.The overrich prepared on coating machine to cigarette paper into paper
Dispersion liquid carries out one side coating (coating weight 2.5g/m2), vacuum drying afterwards obtains modified cigarette paper products.With blank sample
Contrast, 1.46kN/m is increased to by 1.09kN/m by cigarette paper intensity prepared by method in this example, 10cm smoldering velocities by
61.25 increase to 80.75s, and air permeability reduces by 31% (air permeability is by standard GB/T/T458-2008 measurements).With embodiment 1
Contrast, although the pure plant nano dispersion fluid for being coated with overrich can further improve the intensity of cigarette paper, due to air permeability
It is obvious to reduce, cigarette paper smoldering velocity is substantially reduced, efficiency of combustion declines.It can be seen that pure plant of the present invention is received
Rice combustion adjuvant also is used as fire retardant use in the case where dosage is excessive.The functional group content of the nano combustion improver is 0.65%
(its measuring method " is reported using document in ACS Applied Materials＆Interfaces, 2015,7,5006-5016 "
Method).
Comparative example 2
In the citric acid solution for taking the 28wt% that 1g bleached hardwood pulp is added to 75mL, the stirring reaction 3 at 150 DEG C
Hour.After reaction terminates, centrifugal sedimentation 8min under reactant mixture 8000rpm is washed with water 3 times repeatedly, the mixing after washing
Thing further removes water-soluble residue by dialysis.Solidliquid mixture after dialysis is high-pressure homogeneous 15 times through 60Mpa, further
Improve its water slurry stability and nanofiber homogeneity, so as to obtain nanofiber combustion adjuvant, be then made into
0.8wt% dispersion liquid.Into paper carrying out one side coating with the dispersion liquid prepared to cigarette paper on coating machine, (coating weight is
0.5g/m2), vacuum drying afterwards obtains modified cigarette paper products.The cigarette paper intensity that method is handled in example is by blank sample
1.08kN/m increase to 1.11kN/m, 10cm smoldering velocities do not have significant change.Its reason is nanofiber in preparation process
The middle citric acid concentration that uses is too low, although causing its diameter of prepared nanofiber still less than 100nm (about 76nm), its
Functional group content only has 0.02% (its measuring method using document " method of report in Cellulose, 21,2587-2598 ").
Too low functional group content can make the substitution of function base uneven, so as to influence its combustion-supporting effect.
Claims (6)
1. a kind of preparation method of cigarette paper, the preparation method comprise the following steps：
1) cellulosic material is utilized, passes through the mineral acid hydrolysis of high concentration, organic acid hydrolysis, solid acid hydrolysis, periodate oxygen
Change, after TEMPO oxidations or carboxy methylation processing, optionally carry out high-pressure homogeneous processing and pure plant nano combustion improver (work(is made
Nanofiber can be changed) dispersion liquid, the functionalized nano-fiber, its diameter is about 1-100nm, and length can be 10nm to several micro-
Rice, selected from cellulose nano microcrystalline (cellulose nanocrystals), cellulose nanometer fibril (cellulose
Nanofibrils one kind) or its mixing；
2) it is 0.01%-2% obtained pure plant nano combustion improver dispersion liquid in step 1) to be diluted into mass concentration, is preferably
0.5%-1%；
3) the pure plant nano combustion improver dispersion liquid prepared in step 2) is added to cigarette of being manufactured paper with pulp in the slurry for copying cigarette paper
Paper, the dosage of pure plant nano combustion improver are 0.01%-8%, the preferably 1-3% of over dry stock quality, are made after drying
The cigarette paper being modified through pure plant nano combustion improver.
2. the preparation method of cigarette paper according to claim 1, it is characterised in that alternatively, step 3) is entered as follows
OK：The pure plant nano combustion improver dispersion liquid prepared in step 2) is directly coated with or top sizing is to cigarette paper into paper surface,
The cigarette paper being modified through pure plant nano combustion improver can be made after drying；The coating weight of pure plant nano combustion improver is every square metre
The pure plant nano combustion improver of cigarette paper coating/applying glue is in 0.005-2g, i.e. 0.005-2g/m2, preferably 0.1-1.0g/m2, enter
One step is preferably 0.4-0.6g/m2, the mass concentration of described pure plant nano combustion improver dispersion liquid is 0.01%-2%, preferably
For 0.5%-1%.
3. the preparation method of cigarette paper according to claim 1 or 2, it is characterised in that inorganic described in the step 1)
Acid is selected from sulfuric acid, nitric acid and hydrochloric acid, preferably sulfuric acid；The solid acid is selected from phosphotungstic acid, silica-rich zeolite (ZSM-5), cation
Exchanger resin etc., preferably phosphotungstic acid；The organic acid is multicomponent organic acid, preferably malic acid, tartaric acid or citric acid.
4. the preparation method of cigarette paper according to claim 1 or 2, it is characterised in that according to claim 1
In the preparation method of cigarette paper, other auxiliary agents, such as catalyst etc. are not used.
5. the preparation method of cigarette paper according to claim 1 or 2, it is characterised in that in step 1), the pure plant
The preparation method of nano combustion improver dispersion liquid can select one of following method：
(1) sulphuric acid hydrolysis
Take 1 parts by weight cellulosic material add 10-50 parts by weight mass concentration be 35wt%-72wt% sulfuric acid solution in
35-65 DEG C of reaction 0.5-2 hour, after reaction terminates, mixed solution is placed in fast cooling in ice bath, and by way of centrifugation
The cellulosic material of sulphuric acid hydrolysis is fully washed, is then placed on dialysis, the cellulose constant to pH value in bag filter
Raw material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose；
(2) hydrochloric acid hydrolysis+high-pressure homogeneous processing
Take 1 parts by weight cellulosic material add 10-45 parts by weight mass concentration be 36wt%-38wt% hydrochloric acid solution in
70-100 DEG C of reaction 1-6 hour, reaction are washed the cellulosic material after HCl treatment by way of centrifuging or filtering after terminating
Only, and the cellulose dispersion liquid for 0.1wt%-0.9wt% is diluted with water, the dispersion liquid is then subjected to high-pressure homogeneous processing,
Homogeneous 3-30 times, preferably 45MPa-95MPa under 25MPa-120MPa pressure, homogenization cycles are preferably 6-12 times, described
Cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose；
(3) malic acid hydrolysis+high-pressure homogeneous processing
The cellulosic material of 1 parts by weight is taken, the malic acid that the mass concentration for adding 15-50 parts by weight is 60wt%-90wt% is molten
Liquid reacts 4-16 hours in 80-140 DEG C, reacts the cellulose after malic acid is hydrolyzed by way of centrifuging or filtering after terminating
Raw material is cleaned, and the cellulose dispersion liquid for 0.1wt%-0.9wt% is diluted with water, and is then carried out the dispersion liquid high-pressure homogeneous
Processing, homogeneous 3-20 times, preferably 45MPa-60MPa under 25MPa-100MPa pressure, homogenization cycles are preferably 5-8 times,
The cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose
Element；
(4) tartaric acid hydrolysis+high-pressure homogeneous processing
The cellulosic material of 1 parts by weight is taken, the tartaric acid that the mass concentration for adding 15-55 parts by weight is 60wt%-90wt% is molten
Liquid reacts 4-12 hours in 90-140 DEG C, reacts the cellulose after malic acid is hydrolyzed by way of centrifuging or filtering after terminating
Raw material is cleaned, and the cellulose dispersion liquid for 0.1wt%-0.9wt% is diluted with water, and is then carried out the dispersion liquid high-pressure homogeneous
Processing, homogeneous 3-20 times, preferably 45MPa-60MPa under 25MPa-100MPa pressure, homogenization cycles are preferably 5-8 times,
The cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo pulp, secondary stock, dissolving pulp or microcrystalline cellulose
Element；
(5) citric acid hydrolysis+high-pressure homogeneous processing
The cellulosic material of 1 parts by weight is taken, the mass concentration for adding 10-55 parts by weight is 30wt%-90% citric acid solution
Reacted 4-12 hours in 85-140 DEG C, reaction is washed the cellulosic material after hydrolysis by way of centrifuging or filtering after terminating
Only, upper strata suspension is taken directly to use after can standing, it is also possible to water is diluted to 0.1wt%-0.9wt% cellulose dispersion liquid,
Then the dispersion liquid is subjected to high-pressure homogeneous processing, homogeneous 3-35 times, preferably 45MPa- under 25MPa-120MPa pressure
95MPa, homogenization cycles are preferably 6-12 times, and the cellulosic material is selected from bleached wood pulp, bleaching straw pulp, cotton pulp, jute pulp, bamboo
Slurry, secondary stock, dissolving pulp or microcrystalline cellulose.
6. a kind of cigarette paper, the cigarette paper is prepared into by preparation method as claimed in any of claims 1 to 5
Arrive.
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| CN201610657249.9A CN107724180B (en) | 2016-08-11 | 2016-08-11 | Preparation method of cigarette paper with functions of supporting combustion and reducing CO discharge |
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| CN201610657249.9A CN107724180B (en) | 2016-08-11 | 2016-08-11 | Preparation method of cigarette paper with functions of supporting combustion and reducing CO discharge |
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| CN108914676A (en) * | 2018-07-25 | 2018-11-30 | 佛山市高明区爪和新材料科技有限公司 | A kind of fine and close preparation method for wrapping grey cigarette paper |
| CN110735343A (en) * | 2019-07-17 | 2020-01-31 | 华南理工大学 | Method for preparing long rod-shaped cellulose nanofibrils through pretreatment of lignin-based solid acids |
| CN111521726A (en) * | 2020-04-26 | 2020-08-11 | 云南中烟工业有限责任公司 | Method for measuring cigarette burning gray |
| CN112458797A (en) * | 2020-11-24 | 2021-03-09 | 中国制浆造纸研究院有限公司 | Cigarette filter tip filling paper containing nano-cellulose and preparation method thereof |
| CN112515232A (en) * | 2020-11-26 | 2021-03-19 | 云南中烟工业有限责任公司 | Cut stem treatment method capable of improving whiteness of cigarette ash |
| CN112690492A (en) * | 2020-12-24 | 2021-04-23 | 云南中烟工业有限责任公司 | Cigarette paper, preparation method thereof and application of cigarette paper in adjusting cigarette burning rate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914676A (en) * | 2018-07-25 | 2018-11-30 | 佛山市高明区爪和新材料科技有限公司 | A kind of fine and close preparation method for wrapping grey cigarette paper |
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| CN111521726A (en) * | 2020-04-26 | 2020-08-11 | 云南中烟工业有限责任公司 | Method for measuring cigarette burning gray |
| CN112458797A (en) * | 2020-11-24 | 2021-03-09 | 中国制浆造纸研究院有限公司 | Cigarette filter tip filling paper containing nano-cellulose and preparation method thereof |
| CN112515232A (en) * | 2020-11-26 | 2021-03-19 | 云南中烟工业有限责任公司 | Cut stem treatment method capable of improving whiteness of cigarette ash |
| CN112515232B (en) * | 2020-11-26 | 2022-07-12 | 云南中烟工业有限责任公司 | Cut stem treatment method capable of improving whiteness of cigarette ash |
| CN112690492A (en) * | 2020-12-24 | 2021-04-23 | 云南中烟工业有限责任公司 | Cigarette paper, preparation method thereof and application of cigarette paper in adjusting cigarette burning rate |
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