EP3017113A1 - Production de cpcc ayant différentes formes de cristaux - Google Patents

Production de cpcc ayant différentes formes de cristaux

Info

Publication number
EP3017113A1
EP3017113A1 EP14820568.5A EP14820568A EP3017113A1 EP 3017113 A1 EP3017113 A1 EP 3017113A1 EP 14820568 A EP14820568 A EP 14820568A EP 3017113 A1 EP3017113 A1 EP 3017113A1
Authority
EP
European Patent Office
Prior art keywords
pcc
source
process water
ions
crystal form
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.)
Withdrawn
Application number
EP14820568.5A
Other languages
German (de)
English (en)
Other versions
EP3017113A4 (fr
Inventor
Päivi SOLISMAA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UPM Kymmene Oy
Original Assignee
UPM Kymmene Oy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by UPM Kymmene Oy filed Critical UPM Kymmene Oy
Publication of EP3017113A1 publication Critical patent/EP3017113A1/fr
Publication of EP3017113A4 publication Critical patent/EP3017113A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—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
    • D21H17/67—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
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/39—Particle morphology extending in three dimensions parallelepiped-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/40—Particle morphology extending in three dimensions prism-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the invention relates to a method for precipitating calcium carbonate (PCC) in a non-rhombohedral crystal form.
  • the invention also relates to a method and a system for preparing printing paper product comprising said PCC.
  • Printing paper is paper intended to be printed by printing machines and manufactured, for example, for magazines and newspapers.
  • the printing paper may be coated, such as LWC (light weight coated) paper, or uncoated, such as SC (super calendered) paper or newsprint.
  • the main raw material for printing paper is usually cellulose based natural fibre, for example mechanically pulped natural fibre, chemically pulped natural fibre, and/or recycled fibre.
  • cellulose based natural fibre for example mechanically pulped natural fibre, chemically pulped natural fibre, and/or recycled fibre.
  • calcium carbonate is used both as a filler and a coating material, due to factors such as the high brightness of carbonate.
  • Calcium carbonate can be categorized into three different forms according to their crystal structures: the calcite form, the aragonite form and the vaterite form. Calcite form is the most abundant and the most stable in nature, and it exists in several different shapes, such as scalenohedral shape, rhombo- hedral shape, prismatic shape, spherical shape and plate-like shape.
  • PCC has been conventionally produced in its own separate plant, from where the PCC slurry is either conveyed by pumping trough pipelines or transported by tank trucks to paper mills.
  • the PCC is made in the plant in a batch process using clean water, and the reaction takes several hours.
  • PCC used as either fillers or in coating can have significant effects on the optical performance of paper, for example different crystal types of PCC filler exhibit a different response to colour, and the optical performance of the paper can be invaluable in product development. Therefore, each type of PCC has its particular economic value, for example the scalenohedral form gives very good light scattering properties, and thus PCC in various forms is very interesting.
  • There are many methods to prepare different PCC crystal shapes in the batch process for example to perform the precipitation under various conditions such as calcium hydroxide concentration, carbon dioxide concentration, temperature, and/or the to use chemical additives.
  • the invention relates to a novel method for precipitating calcium carbonate (PCC) in a non-rhombohedral crystal form.
  • This invention further relates to a method for preparing printing paper product comprising PCC made by said novel method.
  • This invention further relates to said paper product.
  • the method for precipitating PCC in a non-rhombohedral crystal form is primarily characterized in what will be presented in claim 1 .
  • the method for preparing printing paper product comprising said PCC is primarily characterized in what will be presented in claim 9.
  • the system for preparing said paper product is primarily characterized in what will be presented in claim 12.
  • the method relates especially to continuous process for preparing precipitated calcium carbonate (cPCC).
  • the method makes it possible to prepare PCC in a non- rhombohedral crys- tal form and to purify the process water that is from paper or pulp industry, such as a mechanical pulp mill, a chemical pulp mill, or a paper machine .
  • the method for precipitating calcium carbonate in a non- rhombohedral crystal form comprises:
  • the process water is from a mechanical pulp mill, a chemical pulp mill, or a paper machine. More advantageously, the process water is from a mechanical pulp.
  • the process waters of mechanical pulp mills are normally waters that are circulated for reuse in the same process stage or in a different process stage in the mill. These process waters have been in contact with the wood material or with the recycled fibers, and they contain impurities because of the process. These process waters can be filtered to remove solids, which are normally fibers and other solid matter, so that they can be reused in the plant. In this way PCC is made in the process water which is free of solids. Alternatively, process waters can also be non-filtered. In that case calcium carbonate is precipitated on the solids as a coating. This is advantageous because the coating can passivate the impurities. For example impurities are no longer sticky.
  • the method comprises
  • PCC is precipitated in a continuous process. More preferably, PCC is precipitated by introducing the source of calcium ions and the source of carbonate ions continuously in a flow of the process water. Most preferably, the method is a continuous method for precipitating calcium carbonate (cPCC method). In this continuous method, the process water flows in a pipe and source of the calcium ions and the source of carbonate ions are introduced in the process water during its flow in the pipe. The reaction is instantaneous. Immediately after the second source has been introduced, PCC is formed.
  • cPCC method continuous method for precipitating calcium carbonate
  • the process water is shower water, circulation water, filtrates such as washing filtrate, pressates or similar from chip or pulp handling , in general any process water from a process of a mechanical pulp mill .
  • the process water can be also waters from a chemical pulp mill, or a paper machine.
  • said mechanical pulp is groundwood, pressure groundwood, super pressure groundwood, or thermomechanical pulp.
  • the source of carbonate ions is carbon dioxide
  • the source of calcium ions is milk of lime.
  • the carbon dioxide and milk of lime are injected into the flow of process water.
  • the injection order can be either way.
  • the precipitation is conducted at a starting temperature of 30-80°C. However, adjusting the temperature is not necessary to perform the method.
  • the process waters are normally at this temperature range, because they have absorbed heat in the preceding process.
  • the process waters usually flow at low pressure.
  • the pressure of carbon dioxide which is injected in the form of gas, need not be high.
  • Flue gases which are mixture of carbon dioxide and inert gases, can also be used as the source of carbonate ions.
  • the method for preparing printing paper product comprises:
  • PCC in a non-rhombohedral crystal form to the system, said PCC being made by reacting a source of calcium ions and a source of carbonate ions in process water from paper or pulp industry, such as a mechanical pulp mill, a chemical pulp mill, or a paper machine, and
  • a printing paper product comprising at least said cellulose based material and said PCC in a non-rhombohedral crystal form as filler.
  • the method comprises
  • the cellulose based material is supplied in the form of at least two separate fibre flows to a paper machine, for manufacturing a printing paper product having a layered structure.
  • the PCC is admixed to one flow or more than one flow.
  • Figs. 1A-D show SEM images of PCC, wherein PCC produced by a conventional way in continuous process (Fig. 1A) and PCC produced by a method according to one embodiment (Figs. 1 B-1 D) are presented, and Fig. 2 shows the schematic view of a method according to one embodiment.
  • Fig. 3 shows the general principle of the method.
  • Pulping is a method for converting logs, wood chips or other plant fiber source into so-called paper pulp, which can be then conveyed to a paper mill for further papermaking process.
  • Pulp can be manufactured by mechanical pulping in a mechanical pulp mill or by using semi-chemical or fully chemical methods, for example kraft or sulfite processes, in a chemical pulp mill .
  • Mechanical pulps including, but not limited to, stone groundwood, pressure groundwood, super pressure groundwood, thermo groundwood, refiner mechanical pulp, pressure refiner mechanical pulp, thermomechanical pulp and so on.
  • wood extractives the main compounds thereof identified included sterols, sterol esters, fatty acids, resin acids, steroid ketones, hydrocarbons and triglycerides, are natural components of wood and are liberated from wood into process water in the production of mechanical pulp. When water circulations are closed, these compounds are accumulated in the process water leading to problems in process operation.
  • the PCC is made with process water of a mechanical pulp mill
  • impurities such as wood extractives, carbohydrates and metals
  • 30% of wood extractives can be reduced in the process water, more preferably 50%, even more preferably 75%.
  • 20% of carbohydrates can be reduced, preferably 40%, more preferably 65%.
  • the process water is substantially purified in such a manner that the chemical oxygen demand (COD) in the water can decrease by 70%, preferably 85%, more preferably 95 %.
  • PCC can be produced in a non- rhombohedral crystal form.
  • non-rhombohedral crystal form refers to the crystal shapes that belong to calcite form family, which is the most stable crystal form of calcium carbonate, but these crystal forms of calcite are not rhombohedral.
  • the examples of non-rhombohedral crystal form are scalenohedral shape, prismatic shape and plate-like shape.
  • Still another aspect of the method is to manufacture paper products comprising PCC in a non-rhombohedral crystal form, said PCC is produced by precipitating calcium carbonate in process water from paper or pulp industry, such as a mechanical pulp mill, a chemical pulp mill, or a paper machine.
  • the printing paper product comprises wood fibres as the main raw material.
  • the content of cellulose based material in the printing paper product, calculated as dry content, is advantageously not higher than 80 w-% and more advantageously not higher than 70 w-%, but preferably at least 50 w-%.
  • at least 30 wt.% or at least 40 wt.%, more preferably at least 50 wt.% or at least 60 wt. %, and most preferably at least 80 wt. % or at least 90 wt.% of the cellulose based material is wood based.
  • the printing paper product may advantageously comprise mechanical pulp, i.e. mechanically pulped cellulose based particles and/or fibres.
  • the mechanical pulp is preferably selected from thermomechanical pulp (TMP), chemi- thermomechanical pulp (CTMP), bleached chemithermomechanical pulp (BCTMP), pressurized ground wood (PGW), ground wood (GW), refiner mechanical pulp (RMP), recovered fibre (RCF), or mixtures of these.
  • the main raw material is preferably softwood, such as pine, Southern pine, and/or spruce.
  • the main raw material of natural fibre is spruce.
  • the amount of the mechanical pulp is at least 30 wt.% or at least 40 wt.%, more preferably at least 50 wt.% or at least 60 wt. %, and most preferably at least 70 wt.
  • the printing paper product may also comprise chemical pulp, i.e. chemically pulped cellulose based material.
  • the chemical pulp comprises pine, spruce, birch, eucalyptus, and/or acacia.
  • the printing paper product is paper inten- ded to be printed by printing machines and manufactured, for example, for magazines and newspapers.
  • the printing paper product may be coated, such as LWC paper, or uncoated, such as SC paper or newsprint.
  • the filler in the printing paper product comprises precipitated calcium carbonate in a non-rhombohedral crystal form, for example prismatic, scalenohedral or transitional form between cubic and prismatic or scale- nodehral form.
  • the amount of the PCC in the non-rhombohedral crystal form could be 1 -100 dry w-% and is preferably between 10 and 100 dry w-%, more advantageously between 15 and 50 dry w-% and most advantageously between 20 and 40 dry w-% calculated of the total amount of inorganic fillers in the printing paper product.
  • the amount of the PCC in the non-rhombohedral crystal form could be 1 -100 dry w-% and is preferably between 10 and 50 dry w-%, more advantageously between 15 and 40 dry w-% and most advantageously between 20 and 30 dry w-% calculated of the total amount of inorganic fillers in the printing paper product.
  • Fig. 2 shows the general principle of the method.
  • a source of carbonate ions 10, for example carbon dioxide, and a source of calcium ions, for example milk of lime, are introduced into a flow of process water that is from paper or pulp industry, such as a mechanical pulp mill, a chemical pulp mill, or a paper machine, and precipitated calcium carbonate in a non-rhombohedral crystal form 9 is obtained.
  • the order of the source of carbonate ions 10 and the source of calcium ions 1 1 can be either way.
  • Fig. 3 shows an embodiment of the method.
  • the process water coming from a process 8 flows through the pipe and the source of calcium ions and the source of carbonate ions are injected into the flow at point 7 where PCC is formed.
  • the PCC 9 is separated from the flow, and the purified process water is recycled back to the process 8 to the same stage or to a different stage.
  • Fig. 4 shows another embodiment of the method. After precipitating, the water is not recycled back to process 8, but instead to some other steps, for example the feed into the paper machine, together with impurities coated and passivated by PCC. In this case, PCC is not separated from the flow.
  • the present method can be used in any location in a mechanical pulp mill where process water is available.
  • Existing pipes can be used for precipitating calcium carbonate continuously by adding injection devices for injecting the source of calcium ions and the source of carbonate ions.
  • Example 1 Water samples taken from clean water (sample 1 ), clear filtrate of a paper machine (sample 2), washing filtrate of a groundwood mill (sample 3) and circulation water of a groundwood mill (sample 4) were used. Samples were introduced into a system at a flow rate of 2 l/s, and a commercially available feeding device TrumpJet (R) was used to feed CO 2 and milk of lime into the sample flow by using pressure 3 bar at mixing water flow rate of 0,5 l/s. Table 1 shows the conditions of the test.
  • FIGs. 1A-1 D The scanning electron microscope (SEM) images of the resulting PCC are shown in Figs. 1A-1 D.
  • PCC made by a conventional method in continuous process, wherein clean water was used had cubic, rhombohedral form, which is known in the prior art.
  • PCC made with clear filtrate from a paper machine had also cubic shape as shown in Fig. 1 B, but not so sharp as with clean water.
  • PCC produced with process water of a mechanical pulp mill did not contain any cubic particles, instead it was more like prismatic and scalenohedral in shape, as shown in Fig. 1 C, or showed the tendency to prismatic and/or scalenohedral shape, as shown in Fig. 1 D.
  • Table 2 shows the result of examining the contents in the water phase of the samples before and after the precipitation. Detailed analysis on the change of carbohydrates in the water phase is shown in Chart 1 .
  • PCC contents in PCC were also examined. As shown in Chart 4, a lot of galacturonic acid (pectin) was found in PCC.
  • PCC from washing filtrate from a groundwood mill contained 2 % of it, from circulation water from a groundwood mill 1 % and from paper machine clear filtrate 0,25 %.
  • the method is not limited solely to the examples presented in Figs. 1 -2 and in the above description, but it can be modified.
  • the source of the process water is not limited to that from a mechanical pulp mill, and any process water from paper or pulp industry, such as a mechanical pulp mill, a chemical pulp mill, or a paper machine, may apply.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Paper (AREA)

Abstract

L'invention porte sur un procédé pour précipiter du carbonate de calcium (PCC) sous une forme de cristaux non rhomboédrique, lequel procédé met en œuvre : l'introduction d'une source d'ions calcium et d'une source d'ions carbonate dans de l'eau de traitement d'un moulin à pâte mécanique ; et l'agencement des ions carbonate de façon à réagir avec les ions calcium afin de former un carbonate de calcium précipité (PCC) sous une forme de cristaux non rhomboédrique. Cette invention porte également sur un procédé pour préparer un produit de papier d'impression comprenant du carbonate de calcium précipité réalisé à l'aide dudit nouveau procédé. Cette invention porte également sur ledit produit de papier.
EP14820568.5A 2013-07-01 2014-06-27 Production de cpcc ayant différentes formes de cristaux Withdrawn EP3017113A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20135721 2013-07-01
PCT/FI2014/050536 WO2015001182A1 (fr) 2013-07-01 2014-06-27 Production de cpcc ayant différentes formes de cristaux

Publications (2)

Publication Number Publication Date
EP3017113A1 true EP3017113A1 (fr) 2016-05-11
EP3017113A4 EP3017113A4 (fr) 2017-03-01

Family

ID=52143160

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14820568.5A Withdrawn EP3017113A4 (fr) 2013-07-01 2014-06-27 Production de cpcc ayant différentes formes de cristaux

Country Status (2)

Country Link
EP (1) EP3017113A4 (fr)
WO (1) WO2015001182A1 (fr)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833463A (en) * 1972-10-26 1974-09-03 Owens Illinois Inc Method of decolorizing waste process liquid discharged by a paper mill
DE69408807T2 (de) * 1993-12-14 1998-06-18 Ecc Int Ltd Wasser- und Feststoff-Rückgewinnung in einer Papiermühle
GB9507710D0 (en) * 1995-04-13 1995-05-31 Ecc Int Ltd Waste paper treatment process
GB9802999D0 (en) * 1998-02-13 1998-04-08 Ecc Int Ltd Production of products containing precipitated calcium carbonate
MXPA04007332A (es) * 2002-02-02 2005-05-17 Voith Paper Patent Gmbh Metodo para preparar fibras contenidas en una suspension de pulpa.
DE10357437A1 (de) * 2003-12-09 2005-07-07 Voith Paper Patent Gmbh Verfahren zum Beladen einer Faserstoffsuspension und Anordnung zur Durchführung des Verfahrens
DE102007007295A1 (de) * 2007-02-14 2008-08-21 Voith Patent Gmbh Verfahren zum Bilden von Füllstoffen, insbesondere Calciumcarbonat in einer Faserstoffsuspension
ES2549029T3 (es) * 2011-05-16 2015-10-22 Omya International Ag Método para la producción de carbonato de calcio precipitado a partir de desecho de la molienda de pulpa

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2015001182A1 *

Also Published As

Publication number Publication date
EP3017113A4 (fr) 2017-03-01
WO2015001182A1 (fr) 2015-01-08

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