WO2006122921A1 - VERFAHREN ZUR BESTIMMUNG DER LEIMUNGSMITTELKONZENTRATION, DER TEILCHENGRÖßE UND DER TEILCHENGRÖßENVERTEILUNG VON LEIMUNGSMITTELN IN EINEM PAPIERSTOFF - Google Patents
VERFAHREN ZUR BESTIMMUNG DER LEIMUNGSMITTELKONZENTRATION, DER TEILCHENGRÖßE UND DER TEILCHENGRÖßENVERTEILUNG VON LEIMUNGSMITTELN IN EINEM PAPIERSTOFF Download PDFInfo
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- WO2006122921A1 WO2006122921A1 PCT/EP2006/062316 EP2006062316W WO2006122921A1 WO 2006122921 A1 WO2006122921 A1 WO 2006122921A1 EP 2006062316 W EP2006062316 W EP 2006062316W WO 2006122921 A1 WO2006122921 A1 WO 2006122921A1
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- Prior art keywords
- particle
- scattered light
- light intensity
- particles
- particle size
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 228
- 238000009826 distribution Methods 0.000 title claims abstract description 56
- 238000004513 sizing Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229920001131 Pulp (paper) Polymers 0.000 title abstract 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000011156 evaluation Methods 0.000 claims description 9
- 238000010606 normalization Methods 0.000 claims description 9
- 238000009652 hydrodynamic focusing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- FPTLZCGNCUNOGI-UHFFFAOYSA-N N-butyl-4-(butylamino)naphthalene-1-carboxamide Chemical compound C(CCC)N=C(O)C1=CC=C(C2=CC=CC=C12)NCCCC FPTLZCGNCUNOGI-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 39
- 239000000123 paper Substances 0.000 description 33
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 20
- 238000005259 measurement Methods 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 11
- 229920002472 Starch Polymers 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- -1 N- (n-butyl) -4- (n-butylamino) -naphthalic acid imide Chemical class 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UWERUIGPWOVNGG-MDZDMXLPSA-N 3-[(e)-dec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCC\C=C\C1CC(=O)OC1=O UWERUIGPWOVNGG-MDZDMXLPSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- RSPWVGZWUBNLQU-FOCLMDBBSA-N 3-[(e)-hexadec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O RSPWVGZWUBNLQU-FOCLMDBBSA-N 0.000 description 1
- FXOMYJAPSPLGEI-UHFFFAOYSA-N 3-hexadec-8-enyloxolane-2,5-dione Chemical class CCCCCCCC=CCCCCCCCC1CC(=O)OC1=O FXOMYJAPSPLGEI-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000004125 X-ray microanalysis Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- ZBQZBWKNGDEDOA-UHFFFAOYSA-N eosin B Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C(O)C(Br)=C1OC1=C2C=C([N+]([O-])=O)C(O)=C1Br ZBQZBWKNGDEDOA-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- OSQUFVVXNRMSHL-LTHRDKTGSA-M sodium;3-[(2z)-2-[(e)-4-(1,3-dibutyl-4,6-dioxo-2-sulfanylidene-1,3-diazinan-5-ylidene)but-2-enylidene]-1,3-benzoxazol-3-yl]propane-1-sulfonate Chemical compound [Na+].O=C1N(CCCC)C(=S)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 OSQUFVVXNRMSHL-LTHRDKTGSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
- G01N15/10—Investigating individual particles
- G01N15/14—Electro-optical investigation, e.g. flow cytometers
- G01N15/1456—Electro-optical investigation, e.g. flow cytometers without spatial resolution of the texture or inner structure of the particle, e.g. processing of pulse signals
- G01N15/1459—Electro-optical investigation, e.g. flow cytometers without spatial resolution of the texture or inner structure of the particle, e.g. processing of pulse signals the analysis being performed on a sample stream
-
- G01N15/1433—
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/34—Paper
- G01N33/343—Paper paper pulp
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Definitions
- the invention relates to a method for determining the sizing agent concentration, the particle size and the particle size distribution of natural and / or synthetic sizing agents in a paper stock or in the white water of a paper machine.
- Impurity particles are mostly hydrophobic and sticky. They come for example from recycled waste paper and run in the papermaking process to deposits in the ma- "machines. In order to push back the negative influence of impurities on the manufacture of paper and fix it fixative dosed to the paper stock. This achieves that the contaminants to the cellulose fibers
- the amount of fixing agent required in each case is then determined by means of an analysis of the paper stock or the white water for the presence of contaminant particles.
- this method only provides a sufficiently accurate particle size distribution if the sample either contains only one type of particle or has several types of particles, but these have an approximately equal dyeability for the fluorescent dye used and a comparable quantum yield. Since these conditions are rarely met in practice, the fluorescence-optical measuring method described does not provide a practically reliable method for determining the particle size distribution in a sample having a plurality of different types of particles. Another disadvantage is that several different types of particles can not be distinguished. So you can not adjust the addition in kind and quantity to the respective conditions.
- DE-A 4040 463 discloses a measuring method for determining the number and size of resin particles in a pulp, in which a pulp suspension is first prepared, the resin particles are separated off by filtration, the resin particles are marked with a fluorescent dye, and then separated, excites light emission, detects the light signals, and evaluates the signals for counting and sizing the resin particles.
- the fluorescent dye used is N- (n-butyl) -4- (n-butylamino) -naphthalic acid imide.
- S (Ti) 1 F (Ti)) is spanned, each associated with a particle type (AK), each area (BK) at least a local maximum of the frequency of the value pairs (S (Ti) 1 F (Ti)) in the space (R) for the particle type (AK), the relative H frequency of the fluorescent light intensity values (F (Ti)) for each particle type (AK), the relative particle size distribution for each particle type (AK) from the relative frequency of the fluorescent light intensity values (F (Ti)) for the corresponding particle type (AK) is calculated, the relative particle size distributions for the individual types of particles (AK) using the location of the areas (BK) in the three-dimensional space (R), from the scattered light intensity values (S (Ti)), the fluorescent light intensity values (F (Ti)) and The frequency of the pairs of values (S (Ti) 1 F (Ti)) is spanned, normalized to each other, and thus a common relative particle size distribution for the particles (Ti) of all particle types (AK) is
- This method is used in particular for determining the particle size distribution of hydrophobic contaminant particles in the pulp or in the white water of paper machines and used to control the dosage of fixatives to the pulp by generating a control signal corresponding to the common relative particle size distribution and metering the amount of fixer needed is made due to this control signal.
- sizing agent In the sizing of paper, at least one sizing agent is added to the paper stock and then dewatered on the wire of a paper machine with formation of sheets.
- Suitable engine sizes are, for example, rosin size, modified rosin size and synthetic sizing agents such as alkenylsuccinic anhydrides (ASA) and alkyldiketenes (AKD).
- ASA and AKD are also referred to as reactive solvents.
- the sizing agents are used in the form of aqueous dispersions in papermaking. Here it is important that the sizing agents dispersed in water are sufficiently retained by the cellulose fibers so that they do not deposit in the paper machines or accumulate in the white water.
- the object of the present invention is to determine the concentration, particle size and particle size distribution of dispersed sizing agents in a paper stock and in the white water of a paper machine.
- the object is achieved according to the invention by a method for determining the sizing agent concentration, the particle size and the particle size distribution of natural and / or synthetic sizing agents in a paper stock or in the white water of a paper machine, when the particles (Ti) of the sizing agent are dyed with a fluorescent dye, the particles (Ti) are singulated in the sample and light is irradiated into the sample along a predetermined irradiation direction, at least one scattered light intensity value (S (Ti)) and / or at least one fluorescent light intensity value (F (Ti)) of each particle (Ti) is measured That is, the particles (Ti) due to the location of their pairs of values (S (Ti) 1 F (Ti)) in a region (BK) in a three-dimensional space (R) consisting of the scattered light intensity values (S (Ti)), the fluorescent light intensity values (F (Ti)) and the frequency of the value pairs (S (Ti) 1 F (Ti)) is
- Suitable sizing agents are natural and / or synthetic sizing agents, e.g. Reactive sizing agent, rosin size, modified rosin size or adhesive polymer dispersions.
- the sizing agents are compounds which are dispersed in water and have, for example, particle sizes in the range of about 0.1 ⁇ m to 100 ⁇ m, preferably 1 ⁇ m to 20 ⁇ m.
- alkyldiketenes and alkenylsuccinic anhydrides are used as engine sizing agents in the manufacture of paper, board and cardboard. These substances are essentially C 1-4 -alkyldiketenes such as stearyl diketene, palmityldiketene, behenyldicene, oleyldiketene and mixtures of the diketenes. They are e.g. by emulsification in water in the presence of cationic starch and an anionic dispersant under the action of shear forces, cf. US 3,223,544 and US 3,130,118. Due to an excess of cationic starch compared to the anionic dispersant, the AKD dispersions thus produced have a cationic charge.
- Alkyl diketenes can also be used together with other sizing agents.
- aqueous, anionically adjusted AKD dispersions are known, which are obtainable, for example, by dispersing AKD in water in the presence of anionic dispersants as the sole stabilizer, cf. WO 00/23651.
- Polymer sizing agents are described, for example, in JP-A 58/115 196, EP-B 257 412 and EP-B 276 770. These are essentially aqueous dispersions of copolymers which are prepared in the presence of starch or degraded starch. Suitable copolymers are, for example, copolymers of styrene and / or acrylonitrile and acrylic acid esters.
- Alkenyl succinic anhydrides are also used in the manufacture of paper and paper products as engine sizing agents in the art.
- the sizing agents are the isomeric 4-, 5-, 6-, 7- and 8-hexadecenylsuccinic anhydrides, decenylsuccinic anhydride, octenylsuccinic anhydride, dodecenylsuccinic anhydride and n-hexadecenylsuccinic anhydride, cf. also CE Farley and RB Water, The Sizing of Paper, Second Edition, (3), Sizing With Alkenyl Succinic Anhydride, TAPPI PRESS, 1989, ISBN 0-89852-051-7.
- Suitable natural sizing agents are rosin size and chemically modified rosin sizes, cf. E. Strazdins, Chapter 1, “Chemistry and Application of Rosin Size” in WF Reynolds (Ed.), “The Sizing of Paper,” Second Edition, Tappi Press (Atlanta, USA), 1989, pp. 1-31 (ISBN 0 -89852-051-7).
- the device outlined in FIG. 2 is used.
- the method of determining the size distribution of sizing agents in a stock or white water is based on at least two types (AK) of fluorescent particles (Ti) in a sample.
- AK fluorescent particles
- Fluorescent particles are those sizing particles that fluoresce naturally or after staining with a fluorescent dye.
- the method according to the invention has at least the following steps:
- the particles (Ti) in the sample are separated. This is preferably done by hydrodynamic focusing of the particles.
- a suspension of the particles to be examined is continuously mixed together with a water stream (so-called envelope stream), and either free-falling or introduced into an enveloped stream cuvette.
- envelope stream water stream
- the sheath flow which flows much faster than the suspension, distributes the particles over a relatively long distance, so that finally the particles predominantly exist as single particles in the sheath flow.
- the light source used is preferably a laser.
- At least one scattered light intensity value (S (Ti)) and at least one fluorescent light intensity value (F (Ti)) are measured from each scattered particle (Ti) passing the light source so as to form at least one pair of values
- the forward scattered light of the sample is recorded, that is to say the scattered light which is emitted in a cone around the irradiation direction of the light from the sample. It is advantageous here to hide the intense excitation light in the irradiation direction.
- the scattered light intensity values (S (Ti)) are therefore preferably taken up in a hollow cone whose inner circumferential surface encloses an angle of at least 5 ° with the irradiation direction and whose outer lateral surface encloses an angle of at most 50 ° with the irradiation direction.
- the scattered light measuring cone can also be subdivided into a plurality of conical layers, ie angle segments, which are then evaluated separately.
- a backscatter signal or a 90 ° scatter signal can be recorded and evaluated.
- each region (BK) SO is determined such that it contains at least one local maximum of the frequency of the value pairs (S (Ti) 1 F (Ti)) for a particle type (AK).
- the relative particle size distributions for the individual particle types (AK) are determined with the aid of the position of the regions (BK) in the three-dimensional space (R), which consists of the scattered light intensity values (S (Ti)), the fluorescence light intensity values (F (F). Ti)) and the frequency of the pairs of values (S (Ti) 1 F (T,)) is clamped on each other normalized. From this, a common relative particle size distribution for all particle types (AK) is then formed.
- the standardization can in principle be carried out with any method, as long as the physical conditions are adequately detected.
- the size of the area is already determined beforehand, for example, to a few percent of the scattered light intensity value (S (Ti)), which is approximately the center of the range of maximum measured value density.
- the chosen range simply has to be large enough to allow reliable averaging by detecting enough value pairs and small enough to minimize the influence of random measurement errors.
- a scattered light area (SLB) of scattered light intensity values (S (Ti)) of predetermined size is determined with upper and lower area limits whose average of the upper and lower area limits equal to the mean of the average values of the scattered light intensity values (S ( Ti)) in the respective scattered light regions (SLB (AK)).
- the now determined scattered light range (SLB) comprises for the different Meßwert capablee, i. Particle species, the areas of greatest or at least very large measured value density. This one for everyone
- SLB scattered light range
- AK scattered light mean values
- a fluorescent light region (FLB (AK)) of fluorescent light intensity values (F (Tj)) is determined for each particle type (AK) of a predetermined size whose value pairs (S (Ti) 1 F (Ti)) are also in the stray light area (SLB) fall.
- the values associated with the scattered light intensity values (S (T,)) in the scattered light region (SLB) are determined
- Fluorescent light intensity values for each particle type (AK), i. for each measured value area.
- N (AK) (M (FLB (A ⁇ ))) / (M (FLB (Ai))).
- value pairs (S (Ti) 1 F (Ti)) in the scattered light range (SLB) are excluded from the evaluation, which has a predetermined deviation for each particle type (AK) from the respective mean value (M (FLB (AK))).
- AK particle type
- M FLB (AK)
- This elimination of presumptive or actual erroneous measurements can in principle take place at any stage of the process, but preferably in the assignment of the particles (Tj) to a certain particle type. If it is found that the value pair (S (Tj) 1 F (Tj)) of a certain particle (Tj) lies clearly outside of each distinguishable measured value area, it is expediently deleted for further evaluation.
- T (O) particles water-dispersed reactive size particles.
- T (O) particles water-dispersed reactive size particles.
- These particles are obtained, for example, by withdrawing a pulp or white water sample from a paper machine and free size particles (eg, resin size or chemically modified resin size particles).
- free size particles eg, resin size or chemically modified resin size particles
- the particles of a sizing agent which is practically insoluble in water are then stained with a preferably lipophilic fluorescent dye, separated in a medium such as water and optically examined as described.
- Other particles which may be present in the paper stock in addition to size particles may also be colored, but these particles absorb the added dye at a different rate and / or contain it in a different concentration entration, so that it is possible to distinguish the stained sizing particles from the other, also stained dispersed particles.
- Suitable fluorescent dyes are, for example:
- N- (n-butyl) -4- (n-butylamino) -naphthalic acid imide (Fluoroi 7GA), Color Index dye (Cl.) Number 40662 (Celluflor), dye of Cl. Number 45400 (Eosin B), 3,3-Ethyloxydicarbocyanine iodide, trisodium salt of 8-hydroxy-1,3,6-pyrene trisulfonic acid, 6-nitro-1,3,3-trimethyl- [2H] -1-benzopyran-2,2-indole (merocyanine 540), 2 [6 (Diethylamino) -3-diethylimino-3H-xanthen-9-yl) benzoic acid (Rhodamine B).
- the particles (T (i)) can be stained with a plurality of different fluorescent dyes, wherein the different dyes emit fluorescent light in different wavelength ranges, which is recorded by one detector per fluorescence band.
- These dyes can be excitable either with the same or only with different excitation frequencies.
- light sources with correspondingly different frequencies are then used, whereby the foci of the light sources either overlap or must be close to each other so that the different recorded fluorescence signals also originate from the same individual particle.
- the particle types (AK) can be distinguished even more reliably from each other.
- the device for determining the size distribution of at least two types (AK) of fluorescent isolated particles (Ti) in a sample has at least one light source, for example a laser, which sends a focused light beam along an axis of irradiation into the sample, the focus of the light beam preferably in the sample, at least one means for receiving at least one scattered light intensity value (S (Ti)) for each particle (Ti), at least one means for receiving at least one fluorescent light intensity value (F (Ti)) for each particle (Ti), and one Evaluation unit to which the scattered light intensity values (S (Ti)) and the fluorescence light intensity values (F (Ti)) for each particle (Ti) are fed, and which is designed such that it can carry out at least the following evaluation steps:
- a device shown schematically in FIG. 2 is preferably provided with an evaluation unit (23, 24, 25) which, in order to normalize the relative particle size distributions for the individual particle types (AK), can still carry out at least the following steps in step (d):
- steps (a) and (b) can also be replaced by a single step in which a stray light region (SLB) is selected without prior determination of the particle-species-specific stray light regions (SLB (AK)).
- SLB scattered light area
- AK particle-species-specific stray light regions
- the device for receiving at least one scattered light intensity value (S (Ti)) for each particle (Ti) is designed and arranged in the device such that the scattered light intensity values (S (Ti)) are recorded in a hollow cone, whose inner circumferential surface coincides with the irradiation axis the light source (10) at an angle of at least 5 °, and the outer circumferential surface with this axis forms an angle of at most 50 °.
- a device with an evaluation unit which excludes such value pairs (S (Ti), F (Ti)) in the scattered light range (SLB) from the evaluation, which has a predetermined deviation from the respective average value (A) for each particle type (AK). M (FLB (AK))).
- S (Ti), F (Ti) in the scattered light range
- A average value
- AK particle type
- M FLB (AK)
- the method and apparatus of the present invention are preferably useful for determining particle size, particle size distribution and sizing agent particle concentration in papermaking. It is thus possible to detect the sizing agent particles present in the pulp or in the white water of paper machines. In particular, they can be used to control or regulate the metering of sizing agents to paper stock in papermaking machines, particularly reactive sizing agents, to avoid overdosing or underdosing. This control is based on a control signal output as a result of the common relative particle size distribution for the various sizing particles.
- FIG. 1 illustrates a schematic representation of a device for separating particles in a sample. Separation of the particles to be optically examined is necessary in the context of the present invention in order to be sure that each individual measured value, ie each value pair (S (Ti) 1 F (Tj)) belongs to a specific particle Ti. Thus, in the process of the present invention, the effects of different dyeability and quantum yield can be estimated and eliminated.
- a sample stream 1 is passed with the particles to be examined through a capillary 2 in a Hüllstromhunt 3, at the end of which a nozzle 4 is located.
- a sheath flow for example simply water, is introduced into the chamber 3 via a hollow-cylindrical line 5 surrounding the capillary 2.
- the sample stream 1 and the sheath flow from the line 5 mix, and due to the higher velocity of the sheath flow, the particles in the Sample stream 1 distributed over a further distance, the sample stream is thus diluted with respect to the particles to be examined.
- This principle is called hydrodynamic focussing.
- the emerging from the nozzle 4 diluted sample stream thus contains the sample particles practically completely isolated.
- this principle of hydrodynamic focusing is particularly suitable for separating the particles in the sample.
- FIG. 2 shows a schematic diagram of a measurement setup according to the present invention.
- a laser 9 supplies excitation light to an objective 10, which focuses the laser light onto a sample 8.
- the focus is preferably in the sample 8, but it can also be outside the same. It is essential only that the intensity of the excitation light in the sample is sufficiently high and that the light cone of the excitation light is not so wide that several sample particles are excited at the same time.
- a photomultiplier 20 captures the excitation light scattered forward in the sample 8 via a lens 18 and forwards the scattered light intensity values or electrical signals proportional thereto via an amplifier 21 to a computer 25.
- the photomultiplier 20 is preceded by a beam stopper 17 and an interference filter 19, the former in front, the latter after the lens 18.
- the interference filter is tuned to the laser and allows only light at the wavelength emitted by the laser to pass.
- the interference filter 19 is used only optionally. It generally improves the signal-to-noise ratio.
- the beam stopper 17 has the function of filtering out the intense fraction of unscatterly continuous excitation light in the cone-shaped scattered light beam 16 coming from the sample 8. Preferably, approximately a core cone with an opening angle of 5 ° is filtered out.
- the measurement of the scattered light happens, moreover, preferably in a hollow cone whose inner circumferential surface with the cone axis an angle of at least 5 °, and whose outer surface encloses an angle of at most 50 ° with the cone axis. Accordingly, the device according to the invention according to FIG.
- the photomultiplier 14 for registering the fluorescent light 11 from the sample 8.
- the fluorescent light from the sample is preferably captured in a 90 ° direction to the incident light beam.
- a lens 12 and an edge filter 13 are also located in the beam path for recording the fluorescence light.
- the photomultiplier 14 passes fluorescence light intensity signals to the computer 25 via an amplifier 22. This contains in each case a multichannel analyzer 23 and 24 for the scattered light and for the fluorescence light. zenzlicht, which sorts the intensity values.
- aqueous dispersion of a sizing sample of a reactive lubricant based on ASA specifically of a C 18 -alkenylsuccinic anhydride which had been stabilized with starch (Amylofax® 00)
- the evaluation and the result of the invention should be clarified.
- Homogenizing ASA in an aqueous solution containing 2.5% by weight of said starch produced a size sizing agent.
- the concentration of ASA in the aqueous, starch-containing dispersion was 12 mg / l.
- the weighed ASA could no longer be completely recovered.
- the working range for this method is therefore between O and 16mg / I ASA.
- FIG. 6 shows the result of this measurement series. The slope of the line corresponds
- the present invention thus provides a method for determining the relative and absolute particle size distribution of various particles in a sample that is simple and fast, and thus particularly suitable for on-line operation.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/913,820 US20080151227A1 (en) | 2005-05-17 | 2006-05-15 | Method for Determining a Sizing Agent Concentration, Particle Size and a Sizing Agent Particle Size Distribution in a Peper Pulp |
CA002608411A CA2608411A1 (en) | 2005-05-17 | 2006-05-15 | Method for determining a sizing agent concentration, particle size and a sizing agent particle size distribution in a paper pulp |
EP06755193A EP1889033A1 (de) | 2005-05-17 | 2006-05-15 | VERFAHREN ZUR BESTIMMUNG DER LEIMUNGSMITTELKONZENTRATION, DER TEILCHENGRÖßE UND DER TEILCHENGRÖßENVERTEILUNG VON LEIMUNGSMITTELN IN EINEM PAPIERSTOFF |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005023326A DE102005023326A1 (de) | 2005-05-17 | 2005-05-17 | Verfahren zur Bestimmung der Leimungsmittelkonzentration, der Teilchengröße und der Teilchengrößenverteilung von Leimungsmitteln in einem Papierstoff |
DE102005023326.0 | 2005-05-17 |
Publications (1)
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WO2006122921A1 true WO2006122921A1 (de) | 2006-11-23 |
Family
ID=36763728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2006/062316 WO2006122921A1 (de) | 2005-05-17 | 2006-05-15 | VERFAHREN ZUR BESTIMMUNG DER LEIMUNGSMITTELKONZENTRATION, DER TEILCHENGRÖßE UND DER TEILCHENGRÖßENVERTEILUNG VON LEIMUNGSMITTELN IN EINEM PAPIERSTOFF |
Country Status (6)
Country | Link |
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US (1) | US20080151227A1 (de) |
EP (1) | EP1889033A1 (de) |
CN (1) | CN101175984A (de) |
CA (1) | CA2608411A1 (de) |
DE (1) | DE102005023326A1 (de) |
WO (1) | WO2006122921A1 (de) |
Families Citing this family (8)
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CN102741683B (zh) * | 2009-12-18 | 2016-06-01 | Fp创新研究中心 | 在线大污染物分析器和方法 |
US9562861B2 (en) * | 2011-04-05 | 2017-02-07 | Nalco Company | Method of monitoring macrostickies in a recycling and paper or tissue making process involving recycled pulp |
CN103076323B (zh) * | 2012-12-28 | 2015-05-06 | 金红叶纸业集团有限公司 | 评估纸张中淀粉分布均匀程度的方法 |
CN103790072B (zh) * | 2014-02-18 | 2016-01-20 | 齐鲁工业大学 | 一种荧光asa造纸施胶剂及其制备方法 |
CN105527281A (zh) * | 2014-11-28 | 2016-04-27 | 芬欧汇川(中国)有限公司 | 造纸白水监测系统和方法 |
DE102016013236B4 (de) | 2016-11-07 | 2020-07-16 | Particle Metrix Gmbh | Vorrichtung und Verfahren zum Messen der Konzentration, der Größe und des Zetapotentials von Nanopartikeln in Flüssigkeiten im Streulichtmodus und im Fluoreszenzmodus |
BR112019026809A2 (pt) | 2017-06-30 | 2020-06-30 | Kemira Oyj | monitoramento de qualidadade da polpa |
CN111272615B (zh) * | 2020-02-21 | 2024-03-08 | 陕西佰傲再生医学有限公司 | 一种凝胶粒径分布检测方法 |
Citations (2)
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DE19700648A1 (de) * | 1997-01-10 | 1998-07-23 | Basf Ag | Verfahren und Vorrichtung zur Bestimmung der Größenverteilung von verschiedenartigen Partikeln in einer Probe |
WO2002050533A1 (en) * | 2000-12-21 | 2002-06-27 | Pulp And Paper Research Institute Of Canada | Method and apparatus for measuring fibre properties |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5408307A (en) * | 1988-07-11 | 1995-04-18 | Omron Tateisi Electronics Co. | Cell analyzer |
DE4040463A1 (de) * | 1990-12-18 | 1992-06-25 | Basf Ag | Messverfahren zur bestimmung von harzteilchen in papierstoffen |
US5650847A (en) * | 1995-06-14 | 1997-07-22 | Erkki Soini | Method and device for determination of parameters of individual microparticles |
JP3308441B2 (ja) * | 1995-12-19 | 2002-07-29 | シスメックス株式会社 | 尿中有形成分分析装置 |
US6320656B1 (en) * | 2000-02-18 | 2001-11-20 | Idexx Laboratories, Inc. | High numerical aperture flow cytometer and method of using same |
-
2005
- 2005-05-17 DE DE102005023326A patent/DE102005023326A1/de not_active Withdrawn
-
2006
- 2006-05-15 CA CA002608411A patent/CA2608411A1/en not_active Abandoned
- 2006-05-15 US US11/913,820 patent/US20080151227A1/en not_active Abandoned
- 2006-05-15 WO PCT/EP2006/062316 patent/WO2006122921A1/de not_active Application Discontinuation
- 2006-05-15 CN CNA2006800170646A patent/CN101175984A/zh active Pending
- 2006-05-15 EP EP06755193A patent/EP1889033A1/de not_active Withdrawn
Patent Citations (2)
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DE19700648A1 (de) * | 1997-01-10 | 1998-07-23 | Basf Ag | Verfahren und Vorrichtung zur Bestimmung der Größenverteilung von verschiedenartigen Partikeln in einer Probe |
WO2002050533A1 (en) * | 2000-12-21 | 2002-06-27 | Pulp And Paper Research Institute Of Canada | Method and apparatus for measuring fibre properties |
Non-Patent Citations (2)
Title |
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KRÖHL T ET AL: "A new laser-optical method for counting colloidally dispersed pitch", NORDIC PULP AND PAPER RESEARCH JOURNAL, STOCKHOLM, SE, vol. 9, no. 1, 1994, pages 26 - 36, XP002231334, ISSN: 0283-2631 * |
MONTE M C ET AL: "Development of a methodology to predict sticky deposits due to the destabilisation of dissolved and colloidal material in papermaking-application to different systems", CHEMICAL ENGINEERING JOURNAL, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 105, no. 1-2, 15 December 2004 (2004-12-15), pages 21 - 29, XP004991875, ISSN: 1385-8947 * |
Also Published As
Publication number | Publication date |
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CA2608411A1 (en) | 2006-11-23 |
US20080151227A1 (en) | 2008-06-26 |
DE102005023326A1 (de) | 2006-11-23 |
CN101175984A (zh) | 2008-05-07 |
EP1889033A1 (de) | 2008-02-20 |
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