FR2775301A1 - A new process for the synthesis of calcium carbonate in contact with cellulosic fibers, for the manufacture of printing paper - Google Patents

Abstract

The process enables the reuse of calcium carbonate from recycled (white water) from manufacturing machines, filtration and treatment with carbon dioxide to form the bicarbonate for subsequent re-precipitation as crystalline calcium carbonate.- DETAILED DESCRIPTION - A new process for obtaining calcium carbonate coated fibers in which the fibers are contacted with CO2 generators and a composition containing Ca++ ions which reacts with CO2 to form a fine precipitate of CaCO3 in situ on the fiber. It comprises: - (1) a stage of production of a primary composition containing Ca(HCO3)2 - (2) a stage of production of a secondary composition containing Ca(OH)2; - (3) a mixing stage of the compositions and the fibers to be treated to form a CaCO3 precipitate.- INDEPENDENT CLAIMS are also included for the new paper product obtained

Description

The present invention relates to a process for the synthesis of carbonate

  calcium in contact with fibers and the new product obtained. It relates more particularly to a process for obtaining fibers integral with particles of calcium carbonate in which the fibers to be treated are brought into contact with means generating carbon dioxide and at least one composition containing Ca ++ ions which can react with carbon dioxide so as to obtain "in fine" a precipitation of calcium carbonate "in situ" on the fibers. The invention also relates to a process for the removal of calcium carbonate from other insoluble compounds contained in different aqueous media and originating in particular from papers to be recycled and deinking inks. It is well known in the various fields concerned by fiber-based products, among which, the field of paper pulp which it is advisable to bring to them fillers, generally mineral, in order to give them certain properties. physical. In addition, given the high cost of producing and processing said fibers, the fillers are presented as a cheaper substitute making it possible to reduce

  the cost of manufacturing the products containing them.

  In particular, in the stationery sector, in addition to the savings generated, the charges give the paper many qualities, including: opacity and whiteness, density and porosity, as well as printability and

to touch.

  Opacity is an essential quality for paper, especially for papers intended for printing and writing where it is desirable that the ink transparent as little as possible on the back of the sheet. For printing and other applications, qualities of whiteness are also sought which fibers do not always have. The stationer, in this case,

add loads.

  The fillers are generally mineral powders; they are added to the fibers before the sheet of paper is formed; we speak of fillers added in the mass during the manufacture of the fibrous suspension which feeds the paper machine (when they are added after the sheet is dried, we speak of pigments added by coating on the dried sheet of paper which comes out of the paper machine, the operation is called "the

sleeping ").

  Usually the fillers are mixed with the fibers

  during the manufacture of the fibrous suspension.

  Synthetic or natural, they are prepared "ex situ", that is to say precipitated or ground, and sieved

  before being used in stationery.

  The main natural fillers are kaolin (aluminum silicate), talc (magnesium silicate) and calcium carbonate; the main synthetic fillers are titanium oxide, aluminum hydroxide, the aluminum sulphate plus lime mixture called "satin white", and precipitated calcium carbonate. Recent developments in paper bonding in an alkaline medium have favored the use, among these different fillers, of both natural and precipitated calcium carbonates, the precipitates taking an increasingly large part, not only thanks to their higher whiteness, but also thanks to their morphological characteristics. The fillers are introduced in variable quantities according to the kinds of paper, between 5 and 35% by weight on average. There is an economic interest in increasing the content of fillers when the paper is sold on the basis of its weight, or by sheet: the high cost of fibers is partially replaced by the lower cost of fillers. However, too high a content of fillers weakens the mechanical performance of the paper, which leads manufacturers to use bonding and retention agents; other chemical additives are also used, among which bonding agents in order to reduce the sensitivity of the sheet to water, drainage agents to facilitate flow during the shaping of

leaf.

  Optimizing the charge rate will mainly be based on the shape and distribution of the mineral crystals in the fibers. Their purity and crystallographic characteristics will influence the

qualities of paper.

  Paper is therefore a composite material, the production of which requires a series of steps using several technologies for mixing raw materials with very different physical and chemical properties, forming a wet sheet by removing water, drying of the wet sheet, the possible treatment of the surface of the sheet, and the recycling of the various waters resulting from the process, called "white waters". If the main raw materials are vegetable fibers and fillers, chemical additives, most of which are expensive, are necessary for the success of each stage; decreasing the quantities is therefore a

  goal for the paper maker.

  Incorporating fillers into fibers is an essential step in the papermaking process. Faced with the many difficulties encountered in carrying out this stage, various processes and products have been proposed in order to improve the impact of the charges, both in

  the papermaking process only in the qualities of the finished product.

  One of the recommended ways consists in preparing "in situ", therefore in the presence of fibers, the fillers, in order to

  retain them better and distribute them in the fibrous mat.

  It is thus known from US-A-2583548, a process consisting of impregnating cellulose fibers with a solution containing calcium chloride, then reacting this salt with sodium carbonate according to the double decomposition reaction of two salts :

CaCl2 + Na2CO3 -> CaCO3 + 2 NaCl.

  The impregnation of calcium chloride in the fibers then makes it possible to precipitate the calcium carbonate in the fibers, or around the fibers. Sodium chloride, a secondary product resulting from the reaction, must be eliminated

  by washing, which complicates the industrial implementation.

  It is also known from US-A-5096539, a method describing according to this same principle, an "in situ" precipitation of calcium carbonate from calcium chloride, this method introducing a step of washing the fibers before adding sodium carbonate in order to eliminate the calcium chloride located outside the fibers and to precipitate more specifically the calcium carbonate in the hollow part of the fibers, the lumen. This process, if it improves the retention and the maintenance of the mechanical properties by favoring the contact between the fibers and therefore the fiber / fiber bonds (since the filler is inside these) calls for successive washings which greatly limit the scope

invention.

  It is also known from Japanese application J60-

  297382 a carbonation process for lime hydroxide according to the reaction: Ca (OH) 2 + CO2 * CaCO3 + H20 In this process, lime hydroxide is brought into contact with fibers. The lime hydroxide is added in solid form. The fibers are present in the form of a suspension, they must have fibrils on their surface to allow the calcium carbonate to be retained later. The whole is mixed with stirring for a time of the order of ten minutes. The carbon dioxide is then blown in with stirring to carbonate the lime. This agitation phase is inevitable; it ensures uniformity of reaction and

  production of uniform calcium carbonate particles.

  The reaction time depends on the proportion of lime added and the concentration of carbon dioxide; it is generally around 30 minutes. This process, if it has the advantage of not requiring a washing step, remains complex to implement continuously. In particular, during the first stage, it is necessary to prepare the milk of lime in contact with the fibers and especially with the fibrils, in a relatively concentrated medium and generally, more by weight, more quicklime than fibers is added. In the second step, which is very delicate to carry out, very significant and decisive agitation is used so that the carbon dioxide injected into the suspension of fibers and slaked lime can react with the lime hydroxide, in order to then form heap of crystals trapping the fibrils. The fibers will be all the better secured to the crystals as these will be in higher concentration. It is also known from US-A-5223090, in application of this same reaction:

Ca (OH) 2 + CO2 -> CaCO3 + H20.

  A process for the synthesis of CaCO3 "in situ" in contact with cellulosic fibers in which calcium is added in powder form in the form of CaCO or Ca (OH) 2 to hollow fibers containing water inside and in the walls. According to this process, the fibers can in no case be in the form of an aqueous suspension of fibers at the time of the addition of the carbon dioxide, the latter having to be added in sufficient quantity to ensure a complete reaction. This step is necessarily carried out in a reactor, under pressure and

  of variable agitation according to the water content of the fibers.

  The product thus obtained at the end of this reaction must then be transferred to integrate the papermaking process or be used as an additive. According to this process, and in order to facilitate the mixing of lime and fibers, it may be preferable to load the fibers in a suspension rich in water, then to centrifuge said suspension in order to remove the water therefrom before proceeding to adding dioxide

  of carbon in a pressurized reactor.

  It is also known from French patent application 2689530, a process for obtaining "in situ" fibers loaded with calcium carbonate in which the application of the reaction scheme implying in the same way as for the two previously cited patents the following two successive stages: bringing the fibers and calcium hydroxide into contact, then adding carbon dioxide. The process described in this French patent application has the same drawbacks as those of the process described in Japanese application J60-297382, that is to say: the need to use a large proportion of fillers so that the calcium carbonate precipitates formed trap the fibrils to secure them, the need for a suspension containing fibers rich in fibrils, but also the use of a powerful mixing device so that the injected gas reacts with

lime hydroxide.

  All the processes described above also have the disadvantage of not allowing a purification of the fillers in order to improve the whiteness: it is indeed impossible in these processes to remove colored impurities possibly present in the bath which will come therefore deposit on the fiber, at the same time as the carbonate, and will therefore limit the whiteness of the paper

thus obtained.

  The processes described above are not directly applicable in the papermaking process because they cannot be integrated into the current manufacturing circuit, either because they require complex washing phases, or because they offer reactions chemical

  delicate gas / liquid / solid type in the presence of fibers.

  At present, there is therefore no process for preparing calcium carbonate "in situ" which is simply integrated into the papermaking process, which makes it possible to obtain a precipitated calcium carbonate "in situ" of great whiteness and rigorous particle size from any source of calcium carbonate, or which applies to a fibrous suspension whose dilution is in accordance with that of the suspensions which supply the

paper machine.

  More generally, at the present time there is no method making it possible to remove calcium carbonate in an aqueous medium and / or to separate this calcium carbonate from other products insoluble in an aqueous medium, in particular old paper de-inking sludge

or from recycled paper.

  The invention makes it possible in particular to solve the problems raised. The method according to the invention is characterized in that it comprises a step for producing a first composition containing calcium bicarbonate, a step for producing a second composition containing calcium hydroxide, a mixing step first and second compositions as well as fibers to be treated so as to cause precipitation of carbonate

  calcium on contact with at least some fibers.

  Preferably, the calcium bicarbonate contained in the first composition is obtained by treatment of

  calcium carbonate by carbon dioxide.

  According to a first variant of the invention, the Ca ++ ions come for at least part of a charged water

in calcium carbonate.

  According to another variant of the invention, the Ca ++ ions come for at least part of a lime solution. In order to remove the impurities, the first and / or the second composition are preferably filtered before mixing. The calcium carbonate used to prepare the first composition according to the invention which may be of any origin, natural calcium carbonate of indifferent purity, fine particles present in recovered water or any other source, is preferably present in the form of '' an aqueous suspension containing between 0.5 g / l and 10 g / l, preferably between 1.5 g / l and 3 g / l and

more particularly 2 g / l.

  Preferably, the carbon dioxide is injected in the form of pure gas, or diluted to a total pressure of

  order of atmospheric pressure or higher.

  Preferably, the second composition according to the invention is an aqueous suspension of lime, the concentration of calcium hydroxide being between 1 g / l and 10 g / l, preferably between 1.5 g / l and 2, 5 g / l and more particularly 2 g / l (before filtration). The most judicious concentration corresponds to a concentration slightly higher than the solubility limit of calcium hydroxide in an aqueous medium at the temperature and pressure conditions used, so that the lime solution resulting from filtration

  preferential is saturated.

  According to a variant of the invention, when using a paper-making machine to make paper from fibers, said machine rejecting waste water called "white water", the first composition comprises at least one part of the "white water" from the machine for manufacturing

paper.

  According to another variant of the invention, when using a paper-making machine for making paper from fibers, the said machine rejecting waste water called "white water", the second composition comprises at least part of the "white water" from the paper making machine Preferably, when using a paper making machine to make paper from fibers, the said machine discharging waste water, called " white water ", the method according to the invention comprises a step of separating the" white water "into two parts by filtration, the unfiltered part being called" charged water ", the filtered part being called" clear water ", a step d use of "laden waters" to make the first composition, a 1 step in using "clear waters" to make the second composition. The "charged water" contains very fine calcium carbonate particles, the adjustment of the quantity of calcium carbonate necessary is carried out by adding calcium carbonate of any quality. The quality of the lime hydroxide added to the "clear waters" to make the second composition is

she too.

  It is particularly advantageous in the process according to the invention in which the first composition is a solution of calcium bicarbonate, and the second composition is a solution of lime water, to filter said compositions before mixing, so as to eliminate in particular the insoluble residues colored before the precipitation of calcium carbonate and to obtain a calcium carbonate, with a whiteness at least equal to 95

(according to the degree of ISO whiteness).

  The process according to the invention applies to any type of fibers used in stationery, whatever their

nature and their degree of refinement.

  Preferably, the fibers to be treated will be in the form of a suspension of fibers in water containing between 1 to 15% by weight of fibers and more

  preferably, between 5 and 10% by weight of fibers.

  The new complex product, according to the invention, contains fibers and fillers crystallized on contact, and is characterized in that the calcium carbonate crystals are fixed to the surface of the fibers, they are unitary and regularly distributed over the whole of the surface of the fibers and not agglomerated or grouped in clusters, they are regular and of a size

between 0.5 and 5 gm.

  According to a variant of the invention, the new complex product is characterized in that its calcium carbonate content is between 2 and 50% by weight relative to the total dry matter and preferably between 2

and 30%.

  According to another aspect, the process according to the invention which relates to a process for removing calcium carbonate from other insolubles contained in the various aqueous media and originating in particular from the papers to be recycled and deinking inks is characterized in that it behaves

  - a step of injecting CO2 into the medium to be treated.

  - a solubilization step of sodium carbonate in bicarbonate. - a step of separation of the calcium bicarbonate formed

  by filtration of the medium after reaction.

  The invention will be better understood with the aid of the following exemplary embodiments, given without limitation, together with the figures which represent: FIG. 1 is a diagram of the process for the synthesis of calcium carbonate in contact with fibers in the process stationer. Figures 2 to 4 are views with a scanning electron microscope (SEM) of the new product according to the invention. Figures 5 to 7 are microscope views

  electronic scanning of a control product.

  The process for the synthesis of calcium carbonate in contact with fibers in the papermaking process, according to the process of the invention, is schematically represented on

Figure 1.

  The "white water" is separated into two parts by filtration in the separator (1); the filtered part free of calcium carbonate forms the "clear water", the unfiltered part, enriched in calcium carbonate,

forms "charged waters".

  "Clear water" is used to make milk of lime. To do this, they pass through the calcium hydroxide mixer (2) where lime is added. The quality of the lime added can be arbitrary: quicklime, slaked lime, lime kiln residues, or ovens burning paper waste for example. The amount of lime is determined so that the milk of lime preferably has a concentration slightly higher than the limit of solubility of lime hydroxide under the operating conditions. The milk of lime is filtered in the lime water filter (3) in order to remove the impurities coming from the added lime as well as the

  residual impurities which can come from recycled water.

  The water loaded with calcium carbonate is adjusted in concentration in the carbonator (4) by adding calcium carbonate of any quality. They are treated with gaseous CO 2 in order to transform the insoluble calcium carbonate into calcium bicarbonate whose solubility is higher according to the well-known reaction:

CaCO3 + CO2 gas + H20 -> Ca (HC03) 2.

  A saturated solution of calcium bicarbonate (soluble) is thus produced, containing from 1 to more than 3 g / l of Ca (HCO3) 2. The solution obtained is filtered in the bicarbonate filter (5) in order to remove insoluble impurities, originating both from recycled water and from added calcium carbonate, thus particularly removing

colored insoluble residues.

  According to another aspect of the invention, a pure or substantially pure calcium carbonate is produced, by transformation of the insoluble calcium carbonate contained in any recovery solution into soluble calcium bicarbonate, then separation on one side of the particles, and on the other of the aqueous solution containing the bicarbonate, which can then be precipitated either on the fibers or "ex situ". This method of obtaining calcium carbonate thus makes it possible to recover the calcium carbonate present in various aqueous media linked (or not) to the stationery, in particular from the papers to be recycled and de-inking sludge. According to this particular mode of the invention, the aqueous medium containing, among other insoluble compounds, calcium carbonate, is treated with CO2, then filtered. The aqueous phase containing the calcium bicarbonate can be treated to provide calcium carbonate which will be added to the separator (1) or may be used elsewhere and in the context of the invention; the aqueous phase containing the calcium bicarbonate can also, after adjusting the concentrations, be added directly to the crystallization tank (6) or be used elsewhere and in the context of

the invention.

  The filtrations thus carried out on the solutions containing the calcium ions, will make it possible subsequently to obtain calcium carbonate crystals of great whiteness. The fibers to which the process applies come from the paper machine upstream of the process, they are present here in the form of an aqueous suspension, they are refined according to the final characteristics required of the paper. The invention applies which

whatever the degree of refinement.

  The solutions containing calcium bicarbonate, lime hydroxide and the fiber suspension are then mixed in the crystallization tank (6), continuously or discontinuously according to the needs and facilities of production. The mixing speed and the mixing time will be varied to optimize the crystallographic forms. The crystallization of calcium carbonate then takes place at the fiber level, according to the following reaction scheme: Ca (HCO3) 2 -> CaC03 + CO2 + H20, the pH being less than 8, the CO2 released during the reaction is immediately consumed wherever it appears with calcium hydroxide depending on the reaction: Ca (OH) 2 + 2 CO2 -> Ca (HCO3) 2 or: Ca (OH) 2 + Ca (HCO3) 2 -> 2CaCO3 + 2H20 L advantage of the product obtained according to the invention, in addition to the whiteness qualities which result from the purification by filtration, is measured by the rate of crystals which are fixed in contact with the fibers and by the characteristics

  morphological of the crystals thus formed (and described below

after).

EXAMPLE 1:

  The following example will better illustrate the invention. Three solutions are prepared: Aqueous solution A = 120 g containing 9.60 grams of

vegetable fibers, i.e. 80 g / l.

  Aqueous solution B = 970 g containing 1.60 grams of

Ca (OH) 2, i.e. 1.60 g / l.

  Aqueous solution C = 1600 g containing 3.5 grams of

Ca (HCO3) 2, i.e. 2.2 g / l.

  Solution B is prepared in a beaker containing 2000 g of water. 6 g of quicklime CaO are added. The mixture is stirred for ten minutes at room temperature. The solution is filtered to remove the residual products in suspension and by dilution, the titer is adjusted to 1.6 g / l of Ca (OH) 2. We

takes 970 g of this solution.

  Solution C is prepared in a reactor containing 2000 g of water at room temperature and fitted with a self-aspirating turbine. 6 g of ground CaCO3 are added at 10 μm and, after closing the reactor, CO2 gas is injected under a pressure of 3 bars and this pressure is maintained for 5 minutes. Then, after decompression and slight vacuum to remove the dissolved CO2, this solution is filtered to remove the residual products in suspension and by dilution, the titer is adjusted to 2.2 g / l of Ca (HCO3) 2. We

  takes 1600 g of this solution.

  A + B + C is mixed in a container with stirring.

No other additive is added.

  The sufficient amount of suspension is taken to make a paper form according to the procedure well known to those skilled in the art. The paper sheet is recovered after drying and the calcium carbonate attached to the fibers is measured in proportion to the amount of calcium carbonate precipitated during the mixing of solutions B and C. The level of calcium carbonate attached to the fibers is%. The form contains 20.2% by weight of calcium carbonate. Figure 2 taken with a scanning electron microscope at a magnification of 503, shows that the new product according to the invention is in the form of a fibrous structure composed of elementary fibers carrying calcium carbonate crystals regularly distributed in the whole product, without the formation of agglomerates or clumps. Figure 3, taken with a magnification of 2500,

  shows that these crystals are unitary and fixed to the fibers.

  Their size is regular, around 3 gm approximately.

  Figure 4, taken with a magnification of 10,000, illustrates the growth of the crystals. These crystals are here

rhombohedral structure.

EXAMPLE 2: comparative example.

  This example was carried out with a commercial calcium carbonate called "precipitate" of SOLVAY origin, product 92 E. In this second example, the filler is simply mixed with the fibers according to the conventional route, although

known to those skilled in the art.

  Aqueous solution A = 120 g containing 9.6 grams of

vegetable fibers, i.e. 80 g / l.

  Aqueous solution B = 2570 g containing 4.30 grams of

carbonate 92 E, or 1.70 g / l.

  A + B is mixed in the same way as in Example 1 and a paper form is made under the same conditions. The paper sheet is recovered after drying and the calcium carbonate retained by the fibers is measured in proportion to the quantity of calcium carbonate precipitated from solution B. The level of calcium carbonate retained by the fibers is 15%, without chemical additive. The form contains

  only 6% by weight of calcium carbonate.

  FIG. 5 taken with a scanning electron microscope at a magnification of 503, shows that the control product is in the form of a fibrous structure composed of elementary fibers carrying agglomerates of calcium carbonate crystals distributed in a manner

  irregular throughout the product.

  Figure 6 taken with a magnification of 2500, shows that the crystals are agglomerated, and of size

irregular.

  Figure 7, taken with a magnification of 10,000, shows that the highly agglomerated crystals trap the fibrils. These crystals are, here, of scalenohedral structure. These examples illustrate the advantage of the bicarbonate route according to the invention compared to the conventional route: The rate of fixation of calcium carbonate on the fibers is higher when the bicarbonate route is adopted. The crystals are unitary, fixed on the wall of the

  fibers and not in clumps or agglomerates.

  The crystals have a rather flat shape. They are uniform in size. This size varies between 0.1 and 4 m and preferably between 0.5 and 5 gm depending, mainly, on the speed of mixing, but also on the concentration of the solutions and the temperature. The crystals are smaller when the mixing speed or temperature is high or when the amount of

calcium carbonate is low.

  Without wishing to be bound by any theory, the Applicant believes that, unlike what happens in the case of precipitation "in situ" from calcium hydroxide alone, it is observed in the process according to the invention that: starting from calcium bicarbonate for

  make carbonate, the reaction takes place in micro-

  areas where the pH is acidic (around 6 at the start of the reaction) and in contact with the fibers. There is a growth of calcium carbonate crystals from germs present on and in the hollow fibers. This assumption is supported by the fact that the calcium carbonate crystals according to the invention are in the form of flat crystals characteristic of a crystal obtained from a supersaturated solution by crystal growth. Conversely, in the case of precipitation of calcium carbonate from Ca (OH) 2, the reaction is carried out in basic medium and precipitation on the fibers is observed by mechanical and non-chemical bonding, therefore by agglomeration. of smaller unit crystals as described in the French patent application

  2689530 and not by crystal growth.

  This difference in product structure could explain the better retention of the charges in the fibers. The method according to the invention is applicable to any paste of mechanical or chemical origin, whatever its degree of refining. It can also be applied to recycled pasta (totally or partially): the fibers or mixture of fibers, recycled or not, must be dissolved as described above, to be

  introduced at the level of the crystallization tank (6).

  As regards the aspect of the invention relating to the elimination of calcium carbonate or to the separation thereof from other insolubles, this follows from the above examples: The calcium carbonate present in the sludge deinking or other is transformed into calcium bicarbonate according to the process described above. The bicarbonate being soluble, it suffices to filter the solution to obtain, on one side, water containing the bicarbonate dissolved in it and, on the other, all the insolubles retained in the filter. This makes it possible to recover the carbonate by making it precipitate again and / or to recover sludge without calcium carbonate according to the use

that we want to make of the invention.

Claims (18)

  1. Method for obtaining fibers integral with particles of calcium carbonate in which the fibers to be treated are brought into contact with means generating carbon dioxide and at least one composition containing Ca ++ ions which can react with the carbon dioxide of so as to obtain "in fine" a precipitation of calcium carbonate "in situ" on the fibers, characterized in that it comprises: - a step for producing a first composition   containing calcium bicarbonate.   - a stage of production of a second composition   containing calcium hydroxide.   a step of mixing the first and second compositions as well as the fibers to be treated so as to generate precipitation of the calcium carbonate   in contact with at least some fibers.   2. Method according to claim 1 characterized in that the calcium bicarbonate contained in the first composition is obtained by treatment of carbonate calcium by carbon dioxide.   3. Method according to claim 1 or 2 characterized in that the Ca ++ ions come from at least one   part of a water loaded with calcium carbonate.   4. Method according to one of claims 1 to 3   characterized in that the Ca ++ ions originate for at   minus part of a lime solution.   5. Method according to one of claims 1 to 4   characterized in that the first composition is filtered before mixing.   6. Method according to one of claims 1 to 5   characterized in that the second composition is filtered before mixing.   7. Method according to one of claims 2 to 6   characterized in that the calcium carbonate is present in the form of an aqueous suspension containing between 0.5 g / l and 10 g / l preferably between 1.5 g / l and 3 g / 1 and more especially 2 g / l.   8. Method according to one of claims 2 to 7   characterized in that the carbon dioxide is injected in the form of pure gas or diluted to a total pressure of   order of atmospheric pressure or higher.   9. Method according to one of claims 1 to 8   characterized in that the second composition is an aqueous suspension of lime, the concentration of calcium hydroxide being between 1 g / l and 10 g / l, preferably between 1.5 g / l and 2.5 g / l and more   particularly 2 g / l (before filtration).   10. Method according to one of claims 1 to 9 in   which uses a paper making machine to make paper from fibers, said machine rejecting waste water called "white water" characterized in that the first composition comprises at least a portion of the "white water" from the machine of paper making.   11. Method according to one of claims 1 to 9 in   which uses a paper making machine to make paper from fibers, said machine rejecting waste water called "white water" characterized in that the second composition comprises at least part of the "white water" from the machine of paper making.   12. Method according to one of claims 1 to 9 in   which uses a paper making machine to make paper from fibers, said machine rejecting waste water called "white water" characterized in that it comprises: - a step of separation into two parts of "white water" "by filtration. The unfiltered part is called "loaded water", the filtered part is called "water clear ".   - a step of using "charged water" to make the first composition.   - a stage of using "clear waters" to make the second composition.   13. Method according to one of claims 1 to 12 in   which the first composition is a calcium bicarbonate solution and the second composition is a lime water solution characterized in that said compositions are filtered before mixing so as to remove in particular the insoluble residues colored before the precipitation of carbonate calcium and to obtain a calcium carbonate with a whiteness at least equal to 95 (according to the degree of ISO whiteness).   14. Method according to one of claims 1 to 13   characterized in that the fibers to be treated are in the form of a suspension of fibers in water containing between 1 to 15% of fibers and more particularly   preferably between 5 and 10% by weight.   15. New complex product containing fibers and fillers crystallized on contact, characterized in that:   - The crystals are attached to the surface of the fibers.   - The crystals are unitary and regularly distributed over the entire surface of the fibers and not agglomerated or grouped in clusters.   - The crystals are regular and of a size included   between 0.1 and 10 pm and preferably between 0.5 and 5 pm.   16. New complex product according to claim 15 characterized in that its calcium carbonate content is between 2 and 50% by weight relative to the material   total dry and preferably between 2 and 20%.   17. New complex product according to claim 15 or 16, characterized in that it is in the form a wet leaf.   18. Application of the new product according to one of the   claims 15 to 17 to loaded paper production   including printing writing papers, newsprint, cigarette paper and fine paper.