EP2058434A1 - Herstellungsverfahren eines Papierblatts, das eine Fixierphase einer Mineralienladung auf Zellulosefasern umfasst - Google Patents
Herstellungsverfahren eines Papierblatts, das eine Fixierphase einer Mineralienladung auf Zellulosefasern umfasst Download PDFInfo
- Publication number
- EP2058434A1 EP2058434A1 EP20080020295 EP08020295A EP2058434A1 EP 2058434 A1 EP2058434 A1 EP 2058434A1 EP 20080020295 EP20080020295 EP 20080020295 EP 08020295 A EP08020295 A EP 08020295A EP 2058434 A1 EP2058434 A1 EP 2058434A1
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- EP
- European Patent Office
- Prior art keywords
- ppm
- fibers
- ions
- paper
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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- 239000000835 fiber Substances 0.000 claims abstract description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 49
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012764 mineral filler Substances 0.000 claims abstract description 31
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 19
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 150000004760 silicates Chemical class 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 56
- 230000008569 process Effects 0.000 claims description 49
- 239000011575 calcium Substances 0.000 claims description 47
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 34
- 229910052791 calcium Inorganic materials 0.000 claims description 33
- 239000007900 aqueous suspension Substances 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 235000010216 calcium carbonate Nutrition 0.000 claims description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 18
- 239000000920 calcium hydroxide Substances 0.000 claims description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims description 12
- 239000008267 milk Substances 0.000 claims description 9
- 210000004080 milk Anatomy 0.000 claims description 9
- 235000013336 milk Nutrition 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000002761 deinking Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- 239000010893 paper waste Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000003657 drainage water Substances 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical class [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 38
- 230000014759 maintenance of location Effects 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 description 13
- 235000011116 calcium hydroxide Nutrition 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 10
- 239000001913 cellulose Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- -1 des ions Chemical class 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000003902 lesion Effects 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0035—Introduction of compounds, e.g. sodium sulfate, into the cycle in order to compensate for the losses of pulping agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
Definitions
- the invention relates to a novel method for producing a paper sheet comprising a step of fixing a mineral filler on cellulosic fibers in aqueous suspension.
- the fixing of the mineral fillers, for example calcium, on the fibers can be done by means of a chemical reaction causing the precipitation of an insoluble chemical compound, for example calcium carbonate, which is fixed on the fibers and fibrils of cellulose. .
- the cellulosic fibers on which these mineral fillers are firmly attached are used for papermaking.
- the entire paper industry is concerned.
- the invention can indeed be applied to the manufacture of papers usually loaded with mineral materials such as printing and writing papers such as coated paper, press papers such as newsprint and light coated paper (intended for magazines ), thin papers such as cigarette paper.
- the invention can also be applied to the manufacture of other types of paper such as absorbent papers for sanitary and domestic use which are not conventionally loaded with mineral materials.
- Cellulosic fibers are paper fibers, short or long.
- the aqueous suspensions of fibers are prepared from any type of pulp: chemical pulp, bleached or unbleached, mechanical or thermomechanical pulp or mixtures of these different pastes.
- the dough can also be obtained by a process of deinking waste paper or waste paper.
- Mineral fillers can be added directly to the manufacture of a sheet of paper.
- mineral fillers Natural or synthetic calcium carbonates (CaCO 3 ) are most often used. They are added to papermaking fibers to improve the characteristics and properties of paper products. Mineral fillers can provide different properties to paper. Because of their crystalline structure and their particular morphology, they bring to the paper, the whiteness, the opacity, improves the thickness etc ... They are of an interesting use on the economic plan, decreasing the cost of the raw materials, being cheaper than fiber.
- CaCO 3 natural or synthetic calcium carbonates
- the difficulty lies in the fixing of these charges to cellulosic fibers and in particular in the strength of the charge-fiber bond.
- the charges do not remain in contact with the fibers during the process of making a sheet of paper.
- the mineral fine particles tend not to remain in the fibrous mat formed by the sheet and some of these particles are found in the process water, recovered and / or rejected.
- This phenomenon is conventional in the manufacture of absorbent papers such as cellulose wadding, which are low-weight papers manufactured at high speed or by a conventional method, that is to say, dried and creped, or by a process using through-blow drying.
- retention agents have been added to better retain the mineral fillers on the fibers.
- the fixing process consists in introducing into a relatively concentrated aqueous suspension of fibers, a first reagent based on one of the cations forming the future precipitate, for example calcium oxide or calcium hydroxide, or slaked lime.
- a first reagent based on one of the cations forming the future precipitate for example calcium oxide or calcium hydroxide, or slaked lime.
- the latter patent describes a method of first impregnating calcium chloride fibers, then reacting the salt with sodium carbonate and then washing to remove sodium chloride.
- the object of the invention is to propose a method that makes it possible to solve the problems encountered with the methods of the prior art.
- the object of the invention is to suppress the addition of retention agents and to eliminate any preparative step of preparation in order to integrate the setting of charges in line or "in situ" in the general process of papermaking.
- the solution of the invention is to use as water reaction medium the waters of the papermaking process, namely the water contained in the aqueous suspension of fibers, for the step of fixing the mineral fillers on the fibers. cellulose.
- the invention therefore consists in using this reservoir of ions present in ionic equilibrium in the aqueous suspension of fibers. It is considered that all the waters of the papermaking process form a single reaction medium for precipitation.
- This new process allows on-line integration of the step of precipitation of mineral fillers on the fibers in the more general papermaking process. It uses all the quantity of the water of the process without treating them particularly. It is fully applicable industrially and avoids the use of additional retention agents.
- the invention relates to a method of manufacturing a sheet of paper.
- the manufacturing composition comprises, in ionic equilibrium, sodium ions and hydrogen carbonate ions.
- the manufacturing composition further comprises calcium and / or magnesium hydrogen carbonates.
- the hydroxide of the inorganic filler is a calcium hydroxide.
- the production composition is obtained from a paste resulting from a process for deinking waste paper.
- the complete alkalimetric titer of the aqueous suspension is between 2 and 30 ° F.
- the starting composition comprises in ionic equilibrium at least alkali metal ions and / or alkaline earth, and hydrogen carbonate ions, carbonates or silicates.
- the manufacturing composition comprises in equilibrium hydrogen carbonate ions and sodium and alkaline earth ions.
- the method of manufacturing a paper sheet comprises, after the step of preparing or supplying the production composition, a step of adding a hydroxide of a mineral filler to fix the mineral filler. on the paper fibers, before the step of forming the sheet.
- the process for producing a sheet of paper according to the invention incorporates, among its essential steps, a step of fixing mineral fillers on the fibers, as described below.
- the invention is based on the use of water from the manufacture of pulp or paper within the papermaking process, as a reservoir of ions and even mineral fillers, potentially precipitable.
- the waters present in a papermaking process such as the manufacturing composition which is an aqueous suspension of cellulosic fibers, comprise a large number of ions in ionic equilibrium. The most frequent are the following: H + , OH - , HCO 3 - (hydrogen carbonate ions), CO 3 2- (carbonate ions), (nSiO 2 ) O 2- (silicate ions), Na + (sodium ion), Ca 2+ (calcium ion), Mg 2+ (magnesium ion).
- These waters also include carbon dioxide from either atmospheric carbon dioxide or groundwater or groundwater which are used in the suspension, either from chemical neutralization with industrial or recovered carbon dioxide.
- the water therefore usually contains carbonates (CO 3 2- ), hydrogen carbonates (HCO 3 - ), and dissolved carbon dioxide, depending on the pH value.
- Water recovered or recycled in paper manufacturing processes contains mineral ions.
- the sodium ions are in larger quantities and are in the form of hydrogen carbonates when the neutralizations inherent to the deinking process are carried out from carbon dioxide.
- the molar ratio of sodium ions to other alkaline earth metal ions is often greater than two. The sodium ion thus participates very actively in the ionic equilibrium.
- the cations are mostly balanced by the presence of hydrogen carbonate ions. This is measured by the complete alkalimetic titer (or TAC). This title is between 2 and 30 ° F.
- TAC complete alkalimetic titer
- aqueous suspension composition of cellulosic fibers that can be used in the invention are given below.
- Other compounds may also precipitate in the form of silicates or metal carbonates according to the composition of the water used, and to be fixed on the fibers.
- Calcium hydroxide is added in soluble form or preferably in the form of highly concentrated milk (lime).
- the milk comprises calcium hydroxide particles having a mean diameter of less than 6 ⁇ m.
- the volume of added calcium hydroxide in the form of milk can be very low, in a ratio of up to 1 per 1000.
- This concentration facilitates the integration of this step online, in the papermaking process and has above all a beneficial effect on the distribution of the crystals on all the fibers. Indeed, thanks to the almost instantaneous reaction of this small volume with the suspension of the fibers, there is a strong temporary basicity concentrated in contact with the fibers, which promotes the chemical bonding of the precipitate on the fibers.
- the pH of the aqueous fiber suspension is generally modified as well as the ionic conditions specific to the formation of the sheet. It is therefore necessary to adjust the pH by neutralizing and stabilizing it.
- This pH adjustment can take place in the aqueous suspension of fibers where the mineral fillers are fixed on the fibers, before the formation of the sheet.
- the gas containing carbon dioxide is then injected into the silo of the sewage water.
- the fibers are then recovered at about 5% and the ionically regenerated waters again containing hydrogen carbonate ions are recycled to 95% in the starting manufacturing composition.
- sodium ions recycled with water from paper manufacturing, have an essential function. They first provide hydrogen carbonate ions for the instantaneous precipitation of calcium carbonate (reaction a)), then instantaneously capture hydrogen carbonate ions from the injected carbon dioxide (reaction e)) to stabilize the pH and regenerate the equilibria. ionic.
- this process is very advantageous and makes it possible to fix mineral fillers on the fibers directly during the process of manufacturing a sheet of paper.
- An aqueous suspension of cellulosic fibers is prepared from virgin fibers suspended in ground water.
- the pH is close to 8.
- the calcium hydroxide particles have an average diameter of less than 6 microns. In less than 60 seconds, the pH stabilizes at 10.7.
- a sample is taken to make a paper form according to the conventional method (Formette Franck). From this suspension, it is possible to produce shaped tablets rich in fixed calcium carbonate. We find a retention rate close to 90%, from a basis weight of 25 g / m 2 , this without adding a retention agent. Above 80 g / m 2 , the retention rate becomes close to 100%.
- the form contains about 11.7% calcium carbonate.
- the pH can be reduced to lower values by injecting into the suspension a gas containing 10% carbon dioxide or more, neutralizing sodium hydroxide, magnesium hydroxide and soluble calcium hydroxide.
- An aqueous suspension of cellulosic fibers is prepared from a suspension of fibers from a recycling or de-inking process of waste paper.
- the pH is close to 8.
- the calcium hydroxide particles in lime milk have an average diameter of less than 6 microns.
- the pH stabilizes at 9.8.
- a sample is taken to make a paper form according to the conventional method (Formette Franck). From this suspension, it is possible to manufacture formlets, rich in fixed calcium carbonate. We find a retention rate close to 90%, from a basis weight of 25 g / m 2 , this without adding a retention agent. Above 80 g / m 2 , the retention rate becomes close to 100%.
- the form contains about 13.5% calcium carbonate.
- the pH can be reduced to lower values by injecting into the suspension a gas containing 10% carbon dioxide or more, neutralizing the alkaline elements, essentially sodium hydroxide.
- An aqueous suspension of cellulosic fibers is prepared from a manufacturing composition containing sodium hydrogencarbonate.
- the pH is around 8.4.
- the pH stabilizes rapidly at 8.8.
- a sample is taken to make a paper form according to the conventional method (Formette Franck). From this suspension, we can manufacture form, and according to the retention rate of the fine cellulose particles rich in fixed calcium carbonate, we find a retention rate mineral loads close to 90%, from a basis weight of 25 g / m 2 , this without add retention agent. Above 80 g / m 2 , the retention rate becomes close to 100%.
- the form contains about 15% calcium carbonate.
- diluted carbon dioxide is injected into the air up to 10%.
- the carbon dioxide is recovered from the boiler combustion fumes. Carbon dioxide essentially reformed sodium hydrogencarbonate.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Table Devices Or Equipment (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Cell Separators (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
L'invention concerne un nouveau procédé de fabrication d'une feuille de papier comprenant une étape de fixation d'une charge minérale sur des fibres cellulosiques en suspension aqueuse. La fixation des charges minérales par exemple le calcium, sur les fibres peut se faire au moyen d'une réaction chimique entraînant la précipitation d'un composé chimique insoluble par exemple le carbonate de calcium, qui vient se fixer sur les fibres et fibrilles de cellulose. Les fibres cellulosiques sur lesquelles sont solidement fixées ces charges minérales sont utilisées pour la fabrication de papier.The invention relates to a novel method for producing a paper sheet comprising a step of fixing a mineral filler on cellulosic fibers in aqueous suspension. The fixing of the mineral fillers, for example calcium, on the fibers can be done by means of a chemical reaction causing the precipitation of an insoluble chemical compound, for example calcium carbonate, which is fixed on the fibers and fibrils of cellulose. . The cellulosic fibers on which these mineral fillers are firmly attached are used for papermaking.
Tout le domaine industriel papetier est concerné. L'invention peut en effet s'appliquer à la fabrication des papiers habituellement chargés en matières minérales tels que les papiers d'impression et écriture comme le papier couché, les papiers de presse comme le papier journal et le papier couché léger (destiné aux magazines), les papiers minces comme le papier à cigarettes.The entire paper industry is concerned. The invention can indeed be applied to the manufacture of papers usually loaded with mineral materials such as printing and writing papers such as coated paper, press papers such as newsprint and light coated paper (intended for magazines ), thin papers such as cigarette paper.
L'invention peut également s'appliquer à la fabrication d'autres types de papiers tels que les papiers absorbants à usage sanitaire et domestique qui ne sont pas classiquement chargés en matières minérales.The invention can also be applied to the manufacture of other types of paper such as absorbent papers for sanitary and domestic use which are not conventionally loaded with mineral materials.
Les fibres cellulosiques sont des fibres papetières, courtes ou longues. Les suspensions aqueuses de fibres sont préparées à partir de tout type de pâte : pâte chimique, blanchie ou écrue, pâte mécanique ou thermomécanique ou les mélanges de ces différentes pâtes. La pâte peut aussi être obtenue par un procédé de désencrage de vieux papiers ou papiers de récupération.Cellulosic fibers are paper fibers, short or long. The aqueous suspensions of fibers are prepared from any type of pulp: chemical pulp, bleached or unbleached, mechanical or thermomechanical pulp or mixtures of these different pastes. The dough can also be obtained by a process of deinking waste paper or waste paper.
On peut directement ajouter des charges minérales dans la fabrication d'une feuille de papier.Mineral fillers can be added directly to the manufacture of a sheet of paper.
Parmi les charges minérales classiquement ajoutées, les carbonates de calcium (CaCO3), naturels ou synthétiques, sont le plus souvent utilisés. On les ajoute aux fibres papetières pour améliorer les caractéristiques et propriétés des produits papetiers. Les charges minérales peuvent fournir différentes propriétés au papier. Du fait de leur structure cristalline et leur morphologie particulière, elles apportent au papier, la blancheur, l'opacité, améliore l'épaisseur etc... Elles sont d'une utilisation intéressante sur le plan économique, diminuant le coût des matières premières, étant moins chères que les fibres.Among the conventionally added mineral fillers, natural or synthetic calcium carbonates (CaCO 3 ) are most often used. They are added to papermaking fibers to improve the characteristics and properties of paper products. Mineral fillers can provide different properties to paper. Because of their crystalline structure and their particular morphology, they bring to the paper, the whiteness, the opacity, improves the thickness etc ... They are of an interesting use on the economic plan, decreasing the cost of the raw materials, being cheaper than fiber.
Mais toute la difficulté réside dans la fixation de ces charges aux fibres cellulosiques et en particulier dans la solidité de la liaison charges-fibres. Habituellement, les charges ne restent pas au contact des fibres lors du procédé de fabrication d'une feuille de papier. En effet, les particules fines minérales ont tendance à ne pas rester dans le matelas fibreux formé par la feuille et une partie de ces particules se retrouve dans les eaux du procédé, récupérées et/ou rejetées.But the difficulty lies in the fixing of these charges to cellulosic fibers and in particular in the strength of the charge-fiber bond. Usually, the charges do not remain in contact with the fibers during the process of making a sheet of paper. Indeed, the mineral fine particles tend not to remain in the fibrous mat formed by the sheet and some of these particles are found in the process water, recovered and / or rejected.
Ce phénomène est classique lors de la fabrication de papiers absorbants tels que la ouate de cellulose, qui sont des papiers de faible grammage fabriqués à grande vitesse soit par un procédé conventionnel, c'est-à-dire séchés et crêpés, soit par un procédé utilisant un séchage par soufflage traversant.This phenomenon is conventional in the manufacture of absorbent papers such as cellulose wadding, which are low-weight papers manufactured at high speed or by a conventional method, that is to say, dried and creped, or by a process using through-blow drying.
En outre, dans le cas où une partie des charges minérales est retenue dans le matelas fibreux, elles se répartissent de manière irrégulière dans l'épaisseur de la feuille de papier.In addition, in the case where a part of the mineral fillers is retained in the fibrous mat, they are distributed unevenly in the thickness of the paper sheet.
Afin de résoudre ce problème, on a ajouté des agents de rétention pour mieux retenir les charges minérales sur les fibres.In order to solve this problem, retention agents have been added to better retain the mineral fillers on the fibers.
Depuis 1945, de nombreuses publications et brevets antérieurs décrivent des procédés de précipitation de charges minérales sur des fibres afin d'améliorer la rétention des charges et éviter l'addition d'agents de rétention. Ces procédés reposent sur des réactions chimiques telles que des réactions d'addition ou de double décomposition. Certains procédés visent plus particulièrement la précipitation de charges minérales dans la partie creuse des fibres afin de ne pas modifier les propriétés mécaniques des fibres et donc du papier, qui sont généralement diminuées par la présence des charges.Since 1945, numerous prior publications and patents disclose methods of precipitating mineral fillers on fibers to improve the retention of fillers and to avoid the addition of retention agents. These methods rely on chemical reactions such as addition or double-decomposition reactions. Some processes are more particularly aimed at the precipitation of mineral fillers in the hollow part of the fibers in order not to modify the mechanical properties of the fibers and therefore of the paper, which are generally diminished by the presence of the fillers.
En règle générale, le procédé de fixation consiste à introduire dans une suspension aqueuse relativement concentrée en fibres, un premier réactif à base de l'un des cations formant le futur précipité, par exemple l'oxyde de calcium ou hydroxyde de calcium ou de la chaux éteinte.As a general rule, the fixing process consists in introducing into a relatively concentrated aqueous suspension of fibers, a first reagent based on one of the cations forming the future precipitate, for example calcium oxide or calcium hydroxide, or slaked lime.
Suivant les procédés décrits par les demandes de brevet
La demande internationale
D'autres demandes de brevet ou brevets révèlent des procédés plus complexes à base de sels de calcium. Une étape supplémentaire est prévue pour éliminer l'un des produits de la réaction de double décomposition. C'est le cas des brevets américains
Ce dernier brevet décrit un procédé consistant à d'abord imprégner les fibres de chlorure de calcium, puis faire réagir ce sel avec du carbonate de sodium et effectuer ensuite un lavage afin d'éliminer le chlorure de sodium.The latter patent describes a method of first impregnating calcium chloride fibers, then reacting the salt with sodium carbonate and then washing to remove sodium chloride.
Le brevet américain
Un grand nombre de charges minérales, précipitables suivant un procédé utilisant une réaction du type double décomposition, sont données dans la description de la demande internationale
Mais tous les procédés de précipitation connus et décrits antérieurement font appel à des moyens chimiques et physiques qui nécessitent des étapes annexes de préparation, telles que la solubilisation des réactifs utilisés, la dilution ou la concentration des suspensions aqueuses de fibres, la filtration ou le lavage pour créer les conditions de précipitation.But all precipitation processes known and described previously use chemical and physical means that require additional stages of preparation, such as solubilization of reagents used, dilution or concentration of aqueous suspensions of fibers, filtration or washing to create the conditions of precipitation.
Ces étapes alourdissent considérablement les procédés de fabrication du papier.These steps add considerably to paper making processes.
En effet, il est nécessaire d'ajouter des équipements industriels périphériques afin de mettre en oeuvre ces étapes : bacs de mélange, réacteurs à forte agitation fonctionnant en discontinu, filtres, etc...In fact, it is necessary to add peripheral industrial equipment in order to implement these steps: mixing tanks, reactors with strong stirring operating discontinuously, filters, etc ...
Les temps de réactions chimiques souvent longs impliquent l'utilisation de tels équipements. De ce fait, il est généralement nécessaire de construire une unité de production pour la préparation de fibres chargées, à côté des installations classiques pour la mise en oeuvre du procédé de fabrication du papier.The often long chemical reaction times involve the use of such equipment. As a result, it is generally necessary to construct a production unit for the preparation of filled fibers, next to conventional installations for carrying out the papermaking process.
Par conséquent, les procédés de l'art antérieur décrits précédemment ne sont pas habituellement utilisés industriellement et ne peuvent pas concurrencer les préparations "ex situ" des charges.Consequently, the prior art methods described above are not usually used industrially and can not compete with the "ex situ" preparations of the charges.
La plupart des procédés actuels de fabrication de papier continuent d'utiliser des suspensions de matières minérales déjà préparées avant leur adjonction à la suspension de fibres. Dans ce cas, des agents de rétention sont incorporés afin de retenir les charges sur les fibres au cours du procédé de fabrication du papier.Most current papermaking processes continue to use previously prepared mineral suspensions prior to their addition to the fiber suspension. In this case, retention agents are incorporated to retain the charges on the fibers during the papermaking process.
L'invention a pour but de proposer un procédé qui permette de résoudre les problèmes rencontrés avec les procédés de l'art antérieur.The object of the invention is to propose a method that makes it possible to solve the problems encountered with the methods of the prior art.
L'invention a pour but de supprimer l'addition d'agents de rétention et d'éliminer toute étape annexe de préparation afin d'intégrer la fixation des charges en ligne ou "in situ" dans le procédé général de fabrication du papier.The object of the invention is to suppress the addition of retention agents and to eliminate any preparative step of preparation in order to integrate the setting of charges in line or "in situ" in the general process of papermaking.
Pour ce faire, l'invention a pour solution d'utiliser comme milieu réactionnel les eaux du procédé de fabrication du papier, à savoir l'eau contenue dans la suspension aqueuse de fibres, pour l'étape de fixation des charges minérales sur les fibres cellulosiques.To achieve this, the solution of the invention is to use as water reaction medium the waters of the papermaking process, namely the water contained in the aqueous suspension of fibers, for the step of fixing the mineral fillers on the fibers. cellulose.
En effet, ces eaux sont un réservoir d'ions et de minéraux qui peuvent potentiellement précipiter.Indeed, these waters are a reservoir of ions and minerals that can potentially precipitate.
L'invention consiste donc à utiliser ce réservoir d'ions présents en équilibre ionique dans la suspension aqueuse de fibres. On considère que l'ensemble des eaux du procédé de fabrication du papier forme un seul milieu réactionnel de précipitation.The invention therefore consists in using this reservoir of ions present in ionic equilibrium in the aqueous suspension of fibers. It is considered that all the waters of the papermaking process form a single reaction medium for precipitation.
Dans la description qui suit, on définira ces eaux par l'expression "une suspension aqueuse de fibres cellulosiques issue d'une fabrication papetière".In the description which follows, these waters will be defined by the expression "an aqueous suspension of cellulosic fibers resulting from papermaking".
Ce nouveau procédé permet une intégration en ligne de l'étape de précipitation des charges minérales sur les fibres dans le procédé plus général de fabrication du papier. Il utilise toute la quantité des eaux du procédé sans les traiter particulièrement. Il est tout à fait applicable industriellement et évite l'utilisation d'agents supplémentaires de rétention.This new process allows on-line integration of the step of precipitation of mineral fillers on the fibers in the more general papermaking process. It uses all the quantity of the water of the process without treating them particularly. It is fully applicable industrially and avoids the use of additional retention agents.
L'invention a pour objet un procédé de fabrication d'une feuille de papier.The invention relates to a method of manufacturing a sheet of paper.
Selon une caractéristique essentielle de l'invention, ce procédé consiste à :
- a) préparer ou fournir une composition de fabrication à base d'eau et d'une pâte de fibres papetières chimique blanchie ou écrue, d'une pâte mécanique ou thermomécanique, ou de leurs mélanges, comprenant en équilibre ionique au moins des ions de métaux alcalins et/ou alcalino-terreux et des ions hydrogénocarbonates, carbonates ou silicates ;
- b) ajouter à ladite composition de fabrication, un hydroxyde d'une charge minérale pour fixer en ligne ladite charge minérale sur les fibres papetières,
- c) injecter le dioxyde de carbone dans la composition de fabrication après fixation de la charge minérale sur les fibres pour ajuster le pH ;
- d) former une feuille de papier humide sur une machine à papier à partir des fibres papetières ainsi chargées en suspension et sécher ladite feuille,
- e) récupérer les eaux d'égouttage de l'étage d) ; et
- f) recycler les eaux ainsi traitées dans la composition de fabrication de l'étape a).
- a) preparing or providing a water-based manufacturing composition and a bleached or unbleached chemical paper mill pulp, a mechanical or thermomechanical pulp, or mixtures thereof, comprising in ionic balance at least metal ions alkaline and / or alkaline-earth metals and hydrogen carbonate ions, carbonates or silicates;
- b) adding to said production composition, a hydroxide of a mineral filler for in-line fixing of said mineral filler on the papermaking fibers,
- c) injecting the carbon dioxide into the manufacturing composition after fixing the inorganic filler on the fibers to adjust the pH;
- d) forming a wet paper sheet on a paper machine from the thus loaded pulp fibers in suspension and drying said sheet,
- e) recover the sewage from stage d); and
- f) recycling the treated water in the manufacturing composition of step a).
Procédé selon la revendication 1, caractérisé en ce qu'il consiste de plus à injecter dans les eaux d'égouttage de l'étape e) un gaz comprenant du dioxyde de carbone pour neutraliser et stabiliser le pH desdites eaux.Process according to claim 1, characterized in that it further consists in injecting into the drainage water of step e) a gas comprising carbon dioxide for neutralizing and stabilizing the pH of said water.
Selon une autre caractéristique de l'invention, la composition de fabrication comprend en équilibre ionique des ions sodium et des ions hydrogénocarbonatesAccording to another characteristic of the invention, the manufacturing composition comprises, in ionic equilibrium, sodium ions and hydrogen carbonate ions.
Selon une autre caractéristique de l'invention, la composition de fabrication comprend de plus des hydrogénocarbonates de calcium et/ou de magnésium.According to another characteristic of the invention, the manufacturing composition further comprises calcium and / or magnesium hydrogen carbonates.
Selon une autre caractéristique de l'invention, l'hydroxyde de la charge minérale est un hydroxyde de calcium.According to another characteristic of the invention, the hydroxide of the inorganic filler is a calcium hydroxide.
Selon une caractéristique avantageuse de l'invention, la composition de fabrication est obtenue à partir d'une pâte issue d'un procédé de désencrage de papiers de récupération.According to an advantageous characteristic of the invention, the production composition is obtained from a paste resulting from a process for deinking waste paper.
Selon encore une autre caractéristique de l'invention, le titre alcalimétrique complet de la suspension aqueuse est compris entre 2 et 30° F.According to yet another characteristic of the invention, the complete alkalimetric titer of the aqueous suspension is between 2 and 30 ° F.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description détaillée qui suit, illustrée par le dessin annexé dans lequel :
- la
figure 1 représente le schéma fonctionnel d'un procédé de fabrication d'une feuille de papier selon l'invention.
- the
figure 1 represents the block diagram of a method of manufacturing a sheet of paper according to the invention.
De manière classique, un procédé de fabrication d'une feuille de papier consiste à :
- préparer ou fournir une composition de fabrication à base d'eau et d'une pâte de fibres papetières chimique blanchie ou écrue, d'une pâte mécanique ou thermomécanique, ou de leurs mélanges, et
- former une feuille de papier en déposant les fibres sur une toile pour former une nappe de fibres qui, dans le cas du papier en ouate de cellulose, est ensuite séchée de manière conventionnelle sur un cylindre chauffé ou encore Yankee puis crêpée, ou séchée suivant un procédé dit de soufflage traversant.
- preparing or providing a water-based manufacturing composition and a bleached or unbleached chemical paper mill pulp, mechanical or thermomechanical pulp, or mixtures thereof, and
- forming a sheet of paper by depositing the fibers on a web to form a web of fibers which, in the case of tissue paper, is then conventionally dried on a heated cylinder or Yankee then creped, or dried in accordance with so-called through-blowing process.
La composition de fabrication de départ comprend en équilibre ionique au moins des ions de métaux alcalins et/ou alcalino-terreux, et des ions hydrogénocarbonates, carbonates ou silicates.The starting composition comprises in ionic equilibrium at least alkali metal ions and / or alkaline earth, and hydrogen carbonate ions, carbonates or silicates.
De préférence, la composition de fabrication comprend en équilibre des ions hydrogénocarbonates et des ions sodium et alcalino-terreux.Preferably, the manufacturing composition comprises in equilibrium hydrogen carbonate ions and sodium and alkaline earth ions.
Selon l'invention, le procédé de fabrication d'une feuille de papier comprend après l'étape de préparation ou de fourniture de la composition de fabrication, une étape d'addition d'un hydroxyde d'une charge minérale pour fixer la charge minérale sur les fibres papetières, avant l'étape de formation de la feuille.According to the invention, the method of manufacturing a paper sheet comprises, after the step of preparing or supplying the production composition, a step of adding a hydroxide of a mineral filler to fix the mineral filler. on the paper fibers, before the step of forming the sheet.
Le procédé de fabrication d'une feuille de papier selon l'invention intègre parmi ses étapes essentielles, une étape de fixation de charges minérales sur les fibres, telle que décrite ci-après.The process for producing a sheet of paper according to the invention incorporates, among its essential steps, a step of fixing mineral fillers on the fibers, as described below.
L'invention repose sur l'utilisation des eaux issues de la fabrication de la pâte ou du papier à l'intérieur du procédé de fabrication du papier, comme réservoir d'ions et même de charges minérales, potentiellement précipitables.The invention is based on the use of water from the manufacture of pulp or paper within the papermaking process, as a reservoir of ions and even mineral fillers, potentially precipitable.
Généralement, les eaux présentes dans un procédé de fabrication de papier, telles que la composition de fabrication qui est une suspension aqueuse de fibres cellulosiques, comprennent un grand nombre d'ions en équilibre ionique. Les plus fréquents sont les suivants : H+, OH-, HCO3 - (ions hydrogénocarbonates), CO3 2- (ions carbonates), (nSiO2)O2- (ions silicates), Na+ (ion sodium), Ca2+ (ion calcium), Mg2+ (ion magnésium).Generally, the waters present in a papermaking process, such as the manufacturing composition which is an aqueous suspension of cellulosic fibers, comprise a large number of ions in ionic equilibrium. The most frequent are the following: H + , OH - , HCO 3 - (hydrogen carbonate ions), CO 3 2- (carbonate ions), (nSiO 2 ) O 2- (silicate ions), Na + (sodium ion), Ca 2+ (calcium ion), Mg 2+ (magnesium ion).
Ces eaux comprennent également du dioxyde de carbone provenant soit du dioxyde de carbone atmosphérique, soit des eaux de la nappe souterraine ou nappe phréatique qui sont utilisées dans la suspension, soit d'une neutralisation chimique par du dioxyde de carbone industriel ou récupéré.These waters also include carbon dioxide from either atmospheric carbon dioxide or groundwater or groundwater which are used in the suspension, either from chemical neutralization with industrial or recovered carbon dioxide.
Les eaux contiennent donc habituellement des carbonates (CO3 2-), des hydrogénocarbonates (HCO3 -), et du dioxyde de carbone dissous, selon la valeur du pH.The water therefore usually contains carbonates (CO 3 2- ), hydrogen carbonates (HCO 3 - ), and dissolved carbon dioxide, depending on the pH value.
Les eaux récupérées ou recyclées dans les procédés de fabrication du papier contiennent des ions minéraux. Dans le cas particulier des eaux issues d'un procédé de désencrage, les ions sodium sont en quantités plus importantes et sont sous la forme d'hydrogénocarbonates lorsque les neutralisations inhérentes au procédé de désencrage sont effectuées à partir de dioxyde de carbone. Dans ce cas, le rapport molaire des ions sodium par rapport à d'autres ions de métaux alcalino-terreux, est souvent supérieur à deux. L'ion sodium participe de ce fait de manière très active aux équilibres ioniques.Water recovered or recycled in paper manufacturing processes contains mineral ions. In the particular case of the waters resulting from a deinking process, the sodium ions are in larger quantities and are in the form of hydrogen carbonates when the neutralizations inherent to the deinking process are carried out from carbon dioxide. In this case, the molar ratio of sodium ions to other alkaline earth metal ions is often greater than two. The sodium ion thus participates very actively in the ionic equilibrium.
D'une manière générale, la suspension aqueuse de fibres cellulosiques issue d'une fabrication papetière comprend :
- entre 20 et 1000 ppm (parties par million) d'ions sodium,
- entre 5 et 200 ppm d'ions calcium, et
- entre 5 et 200 ppm d'ions magnésium.
- between 20 and 1000 ppm (parts per million) of sodium ions,
- between 5 and 200 ppm of calcium ions, and
- between 5 and 200 ppm magnesium ions.
Les cations sont équilibrés en majorité par la présence des ions hydrogénocarbonates. Celle-ci est mesurée par le titre alcalimétique complet (ou TAC). Ce titre est compris entre 2 et 30° F. Les eaux issues d'un procédé de désencrage de vieux papiers, se caractérisent par un TAC relativement élevé, du fait de la présence d'une quantité importante d'ions sodium en équilibre avec les ions hydrogénocarbonates.The cations are mostly balanced by the presence of hydrogen carbonate ions. This is measured by the complete alkalimetic titer (or TAC). This title is between 2 and 30 ° F. The water from a process of deinking waste paper, are characterized by a relatively high TAC, because of the presence of a significant amount of sodium ions in equilibrium with the hydrogen carbonate ions.
Des exemples de composition de suspension aqueuse de fibres cellulosiques pouvant être utilisées dans l'invention, sont donnés ci-après.Examples of an aqueous suspension composition of cellulosic fibers that can be used in the invention are given below.
Une suspension aqueuse de fibres obtenue à partir de pâte vierge et d'eaux provenant de nappe souterraine, a la composition suivante :
- 20 à 100 ppm ou plus d'ions sodium
- 8 à 20 ppm ou plus d'ions magnésium
- 20 à 80 ppm ou plus d'ions calcium
- 100 à 400 ppm ou plus de dioxyde de carbone sous la forme de dioxyde de carbone dissous, ions carbonates et ions hydrogénocarbonates.
- 20 to 100 ppm or more of sodium ions
- 8 to 20 ppm or more of magnesium ions
- 20 to 80 ppm or more of calcium ions
- 100 to 400 ppm or more of carbon dioxide in the form of dissolved carbon dioxide, carbonate ions and hydrogen carbonate ions.
Une suspension aqueuse de fibres obtenue à partir des eaux issues d'un procédé de désencrage, a la composition suivante :
- 150 à 250 ppm ou plus d'ions sodium
- 20 à 80 ppm ou plus d'ions calcium
- 8 à 20 ppm ou plus d'ions magnésium
- 200 à 800 ppm ou plus de dioxyde de carbone sous la forme de dioxyde de carbone dissous, ions carbonates et ions hydrogénocarbonates.
L'invention propose d'utiliser les équilibres ioniques de la suspension aqueuse à base de fibres cellulosiques pour fixer des charges minérales sur les fibres par insolubilisation ou précipitation.
Elle vise plus particulièrement l'utilisation des propriétés des ions hydrogénocarbonates de métaux alcalins et/ou alcalino-terreux qui, en présence d'un hydroxyde de calcium (l'unique réactif), réagissent pour former un précipité de carbonate de calcium qui vient se fixer sur les fibres et fibrilles de cellulose.
Plus précisément, l'invention consiste à utiliser les ions hydrogénocarbonates en équilibre avec les ions sodium, et à un degré moindre avec les ions calcium et magnésium comme source d'ions carbonates (CO3 2-), afin de précipiter un complexe à base essentiellement de carbonate de calcium par addition d'hydroxyde de calcium.
Entre autres, les réactions suivantes se réalisent après addition d'hydroxyde de calcium, au contact des fibres cellulosiques :
a) 2Na HCO3 + Ca (OH)2 + fibres ---> Na2CO3 + 2H2O + CaCO3 - fibres
b) Na2 CO3 + Ca (OH)2 ---> 2 Na OH + CaCO3
Les réactions secondaires suivantes peuvent également apparaître :
c) Ca (HCO3)2 + Ca(OH)2 + fibres ---> 2H2O + 2CaCO3 - fibres
d) Mg (HCO3)2 + 2 Ca(OH)2 ---> Mg(OH)2 + 2H2O + 2CaCO3
- 150 to 250 ppm or more of sodium ions
- 20 to 80 ppm or more of calcium ions
- 8 to 20 ppm or more of magnesium ions
- 200 to 800 ppm or more of carbon dioxide in the form of dissolved carbon dioxide, carbonate ions and hydrogen carbonate ions.
The invention proposes to use the ionic equilibrium of the aqueous suspension based on cellulosic fibers in order to fix inorganic fillers on the fibers by insolubilization or precipitation.
More particularly, it relates to the use of the properties of the alkali metal and / or alkaline earth metal hydrogen carbonate ions which, in the presence of a calcium hydroxide (the only reactant), react to form a precipitate of calcium carbonate which has just occurred. fix on cellulose fibers and fibrils.
More specifically, the invention consists in using hydrogen carbonate ions in equilibrium with sodium ions, and to a lesser extent with calcium and magnesium ions as a source of carbonate ions (CO 3 2- ), in order to precipitate a complex based on essentially calcium carbonate by addition of calcium hydroxide.
Among others, the following reactions take place after addition of calcium hydroxide, in contact with the cellulosic fibers:
a) 2Na HCO 3 + Ca (OH) 2 + fibers ---> Na 2 CO 3 + 2H 2 O + CaCO 3 - fibers
b) Na 2 CO 3 + Ca (OH) 2 ---> 2 NaOH + CaCO 3
The following side reactions may also appear:
c) Ca (HCO 3 ) 2 + Ca (OH) 2 + fibers ---> 2H 2 O + 2CaCO 3 - fibers
d) Mg (HCO 3 ) 2 + 2 Ca (OH) 2 -> Mg (OH) 2 + 2H 2 O + 2CaCO 3
D'autres composés peuvent également précipiter sous la forme de silicates ou de carbonates métalliques selon la composition des eaux utilisées, et venir se fixer sur les fibres.Other compounds may also precipitate in the form of silicates or metal carbonates according to the composition of the water used, and to be fixed on the fibers.
L'hydroxyde de calcium est ajouté sous forme soluble ou de préférence sous forme de lait (lait de chaux) très concentré. Le lait comprend des particules d'hydroxyde de calcium d'un diamètre moyen inférieur à 6 µm.Calcium hydroxide is added in soluble form or preferably in the form of highly concentrated milk (lime). The milk comprises calcium hydroxide particles having a mean diameter of less than 6 μm.
Le volume d'hydroxyde de calcium ajouté sous forme de lait, peut être très faible, dans un rapport pouvant aller jusqu'à 1 pour 1000. Cette concentration facilite l'intégration de cette étape en ligne, dans le procédé de fabrication du papier et a surtout un effet bénéfique sur la répartition des cristaux sur l'ensemble des fibres. En effet, grâce à la réaction quasi instantanée de ce faible volume avec la suspension des fibres, on a une forte basicité temporaire concentrée au contact des fibres, qui favorise l'accrochage chimique du précipité sur les fibres.The volume of added calcium hydroxide in the form of milk can be very low, in a ratio of up to 1 per 1000. This concentration facilitates the integration of this step online, in the papermaking process and has above all a beneficial effect on the distribution of the crystals on all the fibers. Indeed, thanks to the almost instantaneous reaction of this small volume with the suspension of the fibers, there is a strong temporary basicity concentrated in contact with the fibers, which promotes the chemical bonding of the precipitate on the fibers.
Une fois la réaction de précipitation terminée, le pH de la suspension aqueuse de fibres est généralement modifié ainsi que les conditions ioniques propres à la formation de la feuille. Il est donc éventuellement nécessaire d'ajuster le pH en le neutralisant et le stabilisant.Once the precipitation reaction is complete, the pH of the aqueous fiber suspension is generally modified as well as the ionic conditions specific to the formation of the sheet. It is therefore necessary to adjust the pH by neutralizing and stabilizing it.
Pour ce faire, on ajoute un acide tel que du dioxyde de carbone pour amener le pH à la valeur souhaitée. Ceci n'a pas d'influence notable sur les composés précipités.To do this, an acid such as carbon dioxide is added to bring the pH to the desired value. This has no notable influence on the precipitated compounds.
Cette addition de dioxyde de carbone permet en outre de regénérer des hydrogénocarbonates alcalins. La suspension aqueuse retrouve ainsi un équilibre ionique.This addition of carbon dioxide also makes it possible to regenerate alkaline hydrogen carbonates. The aqueous suspension thus regains an ionic balance.
Industriellement, on peut injecter des gaz contenant du dioxyde de carbone récupéré des gaz de combustion de chaudière par exemple, éventuellement enrichi de dioxyde de carbone pur. En effet, en milieu alcalin, le dioxyde de carbone dilué réagit instantanément.Industrially, it is possible to inject gases containing carbon dioxide recovered from boiler combustion gases for example, optionally enriched with pure carbon dioxide. Indeed, in an alkaline medium, the diluted carbon dioxide reacts instantly.
Les réactions suivantes s'effectuent :
e) Na2 CO3 + H2O + CO2 ---> 2 Na HCO3
The following reactions occur:
e) Na 2 CO 3 + H 2 O + CO 2 ---> 2 Na HCO 3
f) 2Na OH + CO2 ---> Na2CO3 + H2O
f) 2Na OH + CO 2 ---> Na 2 CO 3 + H 2 O
Et si le gaz est ajouté en excès, les réactions suivantes se produisent :
g) Mg (OH)2 + 2 CO2 ---> Mg(HCO3)2
h) Ca (OH)2 + 2CO2 ---> Ca(HCO3)2
And if the gas is added in excess, the following reactions occur:
g) Mg (OH) 2 + 2 CO 2 ---> Mg (HCO 3 ) 2
h) Ca (OH) 2 + 2CO 2 ---> Ca (HCO 3 ) 2
L'ensemble de ces réactions permet donc de stabiliser le pH aux valeurs souhaitées.All of these reactions thus make it possible to stabilize the pH at the desired values.
Cet ajustement du pH peut avoir lieu dans la suspension aqueuse de fibres où les charges minérales sont fixées sur les fibres, avant la formation de la feuille.This pH adjustment can take place in the aqueous suspension of fibers where the mineral fillers are fixed on the fibers, before the formation of the sheet.
Mais industriellement, cet ajustement a lieu de préférence après la formation de la feuille, dans les eaux blanches ou eaux d'égouttage récupérées lors de l'étape de formation de la feuille. Ces eaux d'égouttage contiennent des fibres fines et des charges minérales.But industrially, this adjustment takes place preferably after the formation of the sheet, in the white water or sewage water recovered during the step of forming the sheet. These dewatering waters contain fine fibers and mineral fillers.
On injecte alors le gaz contenant du dioxyde de carbone dans le silo des eaux d'égouttage. Les fibres sont ensuite récupérées à raison d'environ 5 % et les eaux regénérées sur le plan ionique comportant à nouveau des ions hydrogénocarbonates sont recyclées à raison de 95 % dans la composition de fabrication de départ.The gas containing carbon dioxide is then injected into the silo of the sewage water. The fibers are then recovered at about 5% and the ionically regenerated waters again containing hydrogen carbonate ions are recycled to 95% in the starting manufacturing composition.
Il est à noter que les ions sodium, recyclés avec les eaux issues d'une fabrication papetière, ont une fonction essentielle. Ils fournissent d'abord des ions hydrogénocarbonates pour la précipitation instantanée du carbonate de calcium (réaction a)), puis captent de manière instantanée les ions hydrogénocarbonates provenant du dioxyde de carbone injecté (réaction e)) afin de stabiliser le pH et regénérer les équilibres ioniques.It should be noted that sodium ions, recycled with water from paper manufacturing, have an essential function. They first provide hydrogen carbonate ions for the instantaneous precipitation of calcium carbonate (reaction a)), then instantaneously capture hydrogen carbonate ions from the injected carbon dioxide (reaction e)) to stabilize the pH and regenerate the equilibria. ionic.
Au moyen du procédé selon l'invention, on peut fixer beaucoup de minéraux au contact des fibres et participer à une amélioration du recyclage des eaux issues des procédés de fabrication du papier. Les étapes relatives au procédé de fixation des charges minérales sur les fibres sont donc intégrées dans le procédé "in situ" de fabrication d'une feuille de papier sans modification de l'équipement ni installations supplémentaires.By means of the process according to the invention, it is possible to fix a lot of minerals in contact with the fibers and to participate in an improvement in the recycling of water from paper manufacturing processes. The steps relating to the process for fixing the mineral fillers on the fibers are therefore integrated into the "in situ" process for manufacturing a sheet of paper without modifying the equipment or additional installations.
De ce fait, ce procédé est très avantageux et permet de fixer des charges minérales sur les fibres directement au cours du procédé de fabrication d'une feuille de papier.As a result, this process is very advantageous and makes it possible to fix mineral fillers on the fibers directly during the process of manufacturing a sheet of paper.
Les exemples qui suivent résultent d'essais en laboratoire et illustrent l'étape de fixation d'une charge minérale sur des fibres papetières à partir de suspensions aqueuses de différentes origines et la fabrication de formettes de papier.The following examples result from laboratory tests and illustrate the step of fixing a mineral filler on paper fibers from aqueous suspensions of different origins and the manufacture of paper forms.
On prépare une suspension aqueuse de fibres cellulosiques à partir de fibres vierges mises en suspension dans une eau de nappe phréatique.An aqueous suspension of cellulosic fibers is prepared from virgin fibers suspended in ground water.
Dans un réacteur de 100 litres, on introduit 100 litres de la suspension aqueuse de fibres ayant la composition chimique suivante : (ppm = parties par million)
- Fibres : 2300 ppm
- Hydrogénocarbonates : 210 ppm
- Calcium : 60 ppm
- Sodium : 25 ppm
- Magnésium : 8 ppm
- Dioxyde de carbone dissous : 5 ppm
- Fibers: 2300 ppm
- Hydrogenocarbonates: 210 ppm
- Calcium: 60 ppm
- Sodium: 25 ppm
- Magnesium: 8 ppm
- Dissolved carbon dioxide: 5 ppm
Le pH est voisin de 8.The pH is close to 8.
Puis sous agitation moyenne, on ajoute 100 grammes d'un lait de chaux concentré à 20 %, soit 20 g de Ca(HO)2 ou 10,8 g de calcium. Les particules d'hydroxyde de calcium ont un diamètre moyen inférieur à 6 microns. En moins de 60 secondes, le pH se stabilise vers 10,7.Then, with medium stirring, 100 grams of a 20% concentrated lime milk, that is 20 g of Ca (HO) 2 or 10.8 g of calcium, are added. The calcium hydroxide particles have an average diameter of less than 6 microns. In less than 60 seconds, the pH stabilizes at 10.7.
Après précipitation, la suspension aqueuse (sans tenir compte de la très faible dilution) a la composition suivante :
- Fibres : 2300 ppm
- Carbonates de calcium : 305 ppm (fixé sur les fibres et fibrilles de cellulose)
- Hydrogénocarbonates/carbonates : 25 ppm
- Calcium : 45 ppm
- Sodium : 25 ppm
- Magnésium : 5 ppm
- Dioxyde de carbone dissous : traces
- Fibers: 2300 ppm
- Calcium Carbonates: 305 ppm (fixed on cellulose fibers and fibrils)
- Hydrogenocarbonates / carbonates: 25 ppm
- Calcium: 45 ppm
- Sodium: 25 ppm
- Magnesium: 5 ppm
- Dissolved carbon dioxide: traces
On prélève un échantillon pour fabriquer une formette de papier selon la méthode classique (Formette Franck). A partir de cette suspension, on peut fabriquer des formettes riches en carbonate de calcium fixé. On trouve un taux de rétention proche de 90 %, à partir d'un grammage de 25 g/m2, ceci sans ajouter d'agent de rétention. Au-delà de 80 g/m2, le taux de rétention devient proche de 100 %. La formette contient environ 11,7 % de carbonate de calcium.A sample is taken to make a paper form according to the conventional method (Formette Franck). From this suspension, it is possible to produce shaped tablets rich in fixed calcium carbonate. We find a retention rate close to 90%, from a basis weight of 25 g / m 2 , this without adding a retention agent. Above 80 g / m 2 , the retention rate becomes close to 100%. The form contains about 11.7% calcium carbonate.
On peut ramener le pH vers des valeurs plus faibles en injectant dans la suspension un gaz contenant 10 % de dioxyde de carbone ou plus, en neutralisant la soude, l'hydroxyde de magnésium et l'hydroxyde de calcium soluble.The pH can be reduced to lower values by injecting into the suspension a gas containing 10% carbon dioxide or more, neutralizing sodium hydroxide, magnesium hydroxide and soluble calcium hydroxide.
Après injection du dioxyde de carbone pour obtenir un pH voisin de 8, la suspension aqueuse a la composition suivante :
- Fibres : 2300 ppm
- Carbonates de calcium : 325 ppm (fixé sur les fibres et fibrilles de cellulose)
- Hydrogénocarbonates/carbonates : 120 ppm
- Calcium : 40 ppm
- Sodium : 25 ppm
- Magnésium : 8 ppm
- Dioxyde de carbone dissous : 30 ppm
- Fibers: 2300 ppm
- Calcium carbonates: 325 ppm (fixed on cellulose fibers and fibrils)
- Hydrogenocarbonates / carbonates: 120 ppm
- Calcium: 40 ppm
- Sodium: 25 ppm
- Magnesium: 8 ppm
- Dissolved carbon dioxide: 30 ppm
De la même manière que précédemment, on peut fabriquer des formettes contenant un peu plus de charges, environ 12,5 %, car le calcium neutralisé s'est déposé sur les fibres. Une injection supplémentaire de dioxyde de carbone permet de retrouver les principales qualités initiales de l'eau, en particulier la composition en calcium et hydrogénocarbonates.In the same way as above, it is possible to manufacture formets containing a little more filler, about 12.5%, because the neutralized calcium was deposited on the fibers. An additional injection of carbon dioxide makes it possible to recover the main initial qualities of the water, in particular the composition of calcium and hydrogenocarbonates.
On prépare une suspension aqueuse de fibres cellulosiques à partir d'une suspension de fibres issues d'un procédé de recyclage ou désencrage de vieux papiers.An aqueous suspension of cellulosic fibers is prepared from a suspension of fibers from a recycling or de-inking process of waste paper.
Dans un réacteur de 100 litres, on introduit 100 litres de la suspension ayant la composition suivante : (ppm = parties par million) :
- Fibres : 2300 ppm
- Hydrogénocarbonates : 450 ppm
- Calcium : 60 ppm
- Sodium : 160 ppm
- Magnésium : 8 ppm
- Dioxyde de carbone dissous : 20 ppm
- Fibers: 2300 ppm
- Hydrogenocarbonates: 450 ppm
- Calcium: 60 ppm
- Sodium: 160 ppm
- Magnesium: 8 ppm
- Dissolved carbon dioxide: 20 ppm
Le pH est voisin de 8.The pH is close to 8.
Puis sous agitation moyenne, on ajoute 100 grammes d'un lait de chaux concentré à 20 %, soit 20 g de Ca(OH)2 ou 10,8 g de calcium. Les particules d'hydroxyde de calcium dans le lait de chaux ont un diamètre moyen inférieur à 6 microns.Then, with medium stirring, 100 grams of a 20% concentrated lime milk, that is 20 g of Ca (OH) 2 or 10.8 g of calcium, are added. The calcium hydroxide particles in lime milk have an average diameter of less than 6 microns.
En moins de 60 secondes, le pH se stabilise vers 9,8.In less than 60 seconds, the pH stabilizes at 9.8.
Après précipitation, la suspension aqueuse (sans tenir compte de la très faible dilution) a la composition suivante :
- Fibres : 2300 ppm
- Carbonates de calcium : 370 ppm (fixé sur les fibres et fibrilles de cellulose)
- Hydrogénocarbonates/carbonates : 250 ppm
- Calcium : 20 ppm
- Sodium : 160 ppm
- Magnésium : 5 ppm
- Dioxyde de carbone dissous : traces
- Fibers: 2300 ppm
- Calcium Carbonates: 370 ppm (fixed on cellulose fibers and fibrils)
- Hydrogenocarbonates / carbonates: 250 ppm
- Calcium: 20 ppm
- Sodium: 160 ppm
- Magnesium: 5 ppm
- Dissolved carbon dioxide: traces
On prélève un échantillon pour fabriquer une formette de papier selon la méthode classique (Formette Franck). A partir de cette suspension, on peut fabriquer des formettes, riches en carbonate de calcium fixé. On trouve un taux de rétention proche de 90 %, à partir d'un grammage de 25 g/m2, ceci sans ajouter d'agent de rétention. Au-delà de 80 g/m2, le taux de rétention devient proche de 100 %. La formette contient environ 13,5 % de carbonate de calcium.A sample is taken to make a paper form according to the conventional method (Formette Franck). From this suspension, it is possible to manufacture formlets, rich in fixed calcium carbonate. We find a retention rate close to 90%, from a basis weight of 25 g / m 2 , this without adding a retention agent. Above 80 g / m 2 , the retention rate becomes close to 100%. The form contains about 13.5% calcium carbonate.
On peut ramener le pH vers des valeurs plus faibles en injectant dans la suspension un gaz contenant 10 % de dioxyde de carbone ou plus, en neutralisant les éléments alcalins, essentiellement la soude.The pH can be reduced to lower values by injecting into the suspension a gas containing 10% carbon dioxide or more, neutralizing the alkaline elements, essentially sodium hydroxide.
On prépare une suspension aqueuse de fibres cellulosiques à partir d'une composition de fabrication contenant de l'hydrogénocarbonate de sodium.An aqueous suspension of cellulosic fibers is prepared from a manufacturing composition containing sodium hydrogencarbonate.
Dans un réacteur de 100 litres, on introduit 100 litres de la suspension ayant la composition chimiques suivante : (ppm = parties par million).
- Fibres : 2280 ppm
- Hydrogénocarbonates : 950 ppm
- Calcium : 65 ppm
- Sodium : 300 ppm
- Dioxyde de carbone dissous : 5 ppm
- Fibers: 2280 ppm
- Hydrogenocarbonates: 950 ppm
- Calcium: 65 ppm
- Sodium: 300 ppm
- Dissolved carbon dioxide: 5 ppm
Le pH est voisin de 8,4.The pH is around 8.4.
Puis sous agitation moyenne, on ajoute 100 grammes d'un lait de chaux concentré à 20 %, soit 20 g de Ca(HO)2 ou 10,8 g de calcium.Then, with medium stirring, 100 grams of a 20% concentrated lime milk, that is 20 g of Ca (HO) 2 or 10.8 g of calcium, are added.
Le pH se stabilise rapidement vers 8,8.The pH stabilizes rapidly at 8.8.
Après précipitation, la suspension aqueuse (sans tenir compte de la très faible dilution) a la composition suivante :
- Fibres : 2300 ppm
- Carbonates de calcium : 420 ppm (fixé sur les fibres et fibrilles de cellulose)
- Hydrogénocarbonates/carbonates : 700 ppm
- Calcium : 3 ppm
- Sodium : 300 ppm
- Dioxyde de carbone dissous : traces
- Fibers: 2300 ppm
- Calcium carbonates: 420 ppm (fixed on cellulose fibers and fibrils)
- Hydrogenocarbonates / carbonates: 700 ppm
- Calcium: 3 ppm
- Sodium: 300 ppm
- Dissolved carbon dioxide: traces
On prélève un échantillon pour fabriquer une formette de papier selon la méthode classique (Formette Franck). A partir de cette suspension, on peut fabriquer des formettes, et selon le taux de rétention des particules fines de cellulose riches en carbonate de calcium fixé, on trouve un taux de rétention des charges minérales proche de 90 %, à partir d'un grammage de 25 g/m2, ceci sans ajouter d'agent de rétention. Au-delà de 80 g/m2, le taux de rétention devient proche de 100 %. La formette contient environ 15 % de carbonate de calcium.A sample is taken to make a paper form according to the conventional method (Formette Franck). From this suspension, we can manufacture form, and according to the retention rate of the fine cellulose particles rich in fixed calcium carbonate, we find a retention rate mineral loads close to 90%, from a basis weight of 25 g / m 2 , this without add retention agent. Above 80 g / m 2 , the retention rate becomes close to 100%. The form contains about 15% calcium carbonate.
Si l'on souhaite obtenir un pH inférieur à 8, on injecte du dioxyde de carbone dilué dans l'air jusqu'à 10 %. On récupère le dioxyde de carbone des fumées de combustion de chaudière. Le dioxyde de carbone reforme essentiellement de l'hydrogénocarbonate de sodium.If it is desired to obtain a pH below 8, diluted carbon dioxide is injected into the air up to 10%. The carbon dioxide is recovered from the boiler combustion fumes. Carbon dioxide essentially reformed sodium hydrogencarbonate.
Claims (11)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP99402058A EP1076132B1 (en) | 1999-08-13 | 1999-08-13 | Paper manufacturing process including a step for fixing of mineral fiuller on cellulosic fibres |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99402058A Division EP1076132B1 (en) | 1999-08-13 | 1999-08-13 | Paper manufacturing process including a step for fixing of mineral fiuller on cellulosic fibres |
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| Publication Number | Publication Date |
|---|---|
| EP2058434A1 true EP2058434A1 (en) | 2009-05-13 |
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| EP99402058A Expired - Lifetime EP1076132B1 (en) | 1999-08-13 | 1999-08-13 | Paper manufacturing process including a step for fixing of mineral fiuller on cellulosic fibres |
| EP20080020295 Ceased EP2058434A1 (en) | 1999-08-13 | 1999-08-13 | Herstellungsverfahren eines Papierblatts, das eine Fixierphase einer Mineralienladung auf Zellulosefasern umfasst |
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| Application Number | Title | Priority Date | Filing Date |
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| EP99402058A Expired - Lifetime EP1076132B1 (en) | 1999-08-13 | 1999-08-13 | Paper manufacturing process including a step for fixing of mineral fiuller on cellulosic fibres |
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| US (1) | US6706148B1 (en) |
| EP (2) | EP1076132B1 (en) |
| AT (1) | ATE415518T1 (en) |
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| DE (1) | DE69939978D1 (en) |
| DK (1) | DK1076132T3 (en) |
| ES (1) | ES2318885T3 (en) |
| NO (1) | NO331185B1 (en) |
| PT (1) | PT1076132E (en) |
| TR (1) | TR200200375T2 (en) |
| WO (1) | WO2001012899A1 (en) |
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| EP1158088A3 (en) * | 2000-05-26 | 2003-01-22 | Voith Paper Patent GmbH | Process and device for treating a fibrous suspension |
| FI109483B (en) * | 2000-11-16 | 2002-08-15 | Andritz Oy | Method and apparatus for treating pulp with filler |
| FR2821095B1 (en) * | 2001-02-16 | 2003-04-11 | Arjo Wiggins Sa | PROCESS FOR OBTAINING A PAPER SHEET CONTAINING CALCITE |
| DE10113998A1 (en) * | 2001-03-22 | 2002-09-26 | Voith Paper Patent Gmbh | Method for loading fibers contained in a fiber suspension with an auxiliary |
| DE10120526A1 (en) * | 2001-04-26 | 2002-10-31 | Voith Paper Patent Gmbh | Process for the production of pulp |
| FR2831565B1 (en) | 2001-10-30 | 2004-03-12 | Internat Paper Sa | NOVEL BLANCHIE MECHANICAL PAPER PULP AND MANUFACTURING METHOD THEREOF |
| FI20055380A7 (en) * | 2005-07-01 | 2007-01-02 | M Real Oyj | Method for coating cellulose particles, coated cellulose particles and their use in paper and board production |
| US7833339B2 (en) * | 2006-04-18 | 2010-11-16 | Franklin Industrial Minerals | Mineral filler composition |
| JP4780461B2 (en) | 2006-07-18 | 2011-09-28 | ヤマハ株式会社 | Keyboard structure of electronic keyboard instrument |
| US8034203B2 (en) | 2007-04-13 | 2011-10-11 | United States Gypsum Company | Gypsum wallboard with improved nail pull strength and the method for making same |
| DE102007019783A1 (en) * | 2007-04-26 | 2008-10-30 | Voith Patent Gmbh | Process for loading fibers of a pulp suspension with calcium carbonate formed from (hydrogen) carbonate compounds |
| DE102007019784A1 (en) * | 2007-04-26 | 2008-10-30 | Voith Patent Gmbh | A method for loading fibers of a pulp suspension with calcium carbonate formed from calcium bicarbonate solution |
| SI2093261T1 (en) | 2007-11-02 | 2013-12-31 | Omya International Ag | Use of a surface-reacted calcium carbonate in tissue paper, process to prepare a tissue paper product of improved softness, and resulting improved softness tissue paper products |
| FI123392B (en) | 2008-02-22 | 2013-03-28 | Upm Kymmene Oyj | Method for Precipitation of Calcium Carbonate in a Fibrous Web Process and Fiber Machine Machine Approach |
| FI125836B (en) | 2013-04-26 | 2016-03-15 | Wetend Tech Oy | Process for providing paper or cardboard pulp with filler and paper or cardboard |
| SE538770C2 (en) | 2014-05-08 | 2016-11-15 | Stora Enso Oyj | Process for making a thermoplastic fiber composite material and a fabric |
| US10711400B2 (en) * | 2015-04-09 | 2020-07-14 | Arizona Board Of Regents On Behalf Of Arizona State University | Carbon dioxide sorbents and structures, methods of use, and methods of making thereof |
| WO2018140252A1 (en) * | 2017-01-26 | 2018-08-02 | Kimberly-Clark Worldwide, Inc. | Treated fibers and fibrous structures comprising the same |
| BR112020005307B1 (en) * | 2018-04-13 | 2021-06-08 | Eldorado Brasil Celulose S/A | processes for the in-situ adjustment of ion concentrations during the fabrication of web materials |
| CN114318937A (en) * | 2020-09-27 | 2022-04-12 | 牡丹江市海洋新材料科技有限责任公司 | Novel method for combined use of soluble silicate, polyaluminium chloride and flocculant in multiple fields |
| CN115491927B (en) * | 2022-09-28 | 2023-11-10 | 福建星城纸业有限公司 | High-strength copy paper and production method thereof |
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- 1999-08-13 AT AT99402058T patent/ATE415518T1/en active
- 1999-08-13 DE DE69939978T patent/DE69939978D1/en not_active Expired - Lifetime
- 1999-08-13 ES ES99402058T patent/ES2318885T3/en not_active Expired - Lifetime
- 1999-08-13 EP EP20080020295 patent/EP2058434A1/en not_active Ceased
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- 2000-07-24 US US10/049,505 patent/US6706148B1/en not_active Expired - Lifetime
- 2000-07-24 TR TR2002/00375T patent/TR200200375T2/en unknown
- 2000-07-24 WO PCT/FR2000/002123 patent/WO2001012899A1/en not_active Ceased
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| ANDREA STETTER: "Paper and Board, 5. Water Circuits", INTERNET CITATION, 15 January 2012 (2012-01-15), pages 1, XP002726065, Retrieved from the Internet <URL:http://onlinelibrary.wiley.com/doi/10.1002/14356007.o18_o13/pdf> [retrieved on 20140620] * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2381356C (en) | 2009-04-28 |
| DE69939978D1 (en) | 2009-01-08 |
| NO20020711L (en) | 2002-04-15 |
| CA2381356A1 (en) | 2001-02-22 |
| ES2318885T3 (en) | 2009-05-01 |
| NO20020711D0 (en) | 2002-02-12 |
| DK1076132T3 (en) | 2009-03-16 |
| TR200200375T2 (en) | 2002-08-21 |
| EP1076132B1 (en) | 2008-11-26 |
| PT1076132E (en) | 2009-02-24 |
| EP1076132A1 (en) | 2001-02-14 |
| WO2001012899A1 (en) | 2001-02-22 |
| US6706148B1 (en) | 2004-03-16 |
| ATE415518T1 (en) | 2008-12-15 |
| NO331185B1 (en) | 2011-10-24 |
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