WO1992017640A1 - Procede et installation de traitement de produits en papier dans un fluide dense sous pression - Google Patents

Procede et installation de traitement de produits en papier dans un fluide dense sous pression Download PDF

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Publication number
WO1992017640A1
WO1992017640A1 PCT/FR1992/000293 FR9200293W WO9217640A1 WO 1992017640 A1 WO1992017640 A1 WO 1992017640A1 FR 9200293 W FR9200293 W FR 9200293W WO 9217640 A1 WO9217640 A1 WO 9217640A1
Authority
WO
WIPO (PCT)
Prior art keywords
dense fluid
pressure
treatment
fluid
paper products
Prior art date
Application number
PCT/FR1992/000293
Other languages
English (en)
French (fr)
Inventor
Maurice Carles
Alain Gouchet
Christian Perre
Original Assignee
Commissariat A L'energie Atomique
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 Commissariat A L'energie Atomique filed Critical Commissariat A L'energie Atomique
Priority to EP92909511A priority Critical patent/EP0578736B1/fr
Priority to DE69212467T priority patent/DE69212467T2/de
Priority to JP4508598A priority patent/JP2987520B2/ja
Publication of WO1992017640A1 publication Critical patent/WO1992017640A1/fr

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Classifications

    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring

Definitions

  • the present invention relates to a process for treating paper products with various chemical substances.
  • Papers in particular papers manufactured industly from wood, undergo damage over time which is due in particular to the degradation of the cellulose molecules by hydrolysis reactions and / or d oxidation, leading to the accumulation of acidic substances which contribute to the phenomenon of paper degradation with loss of mechanical strength. Paper documents such as books, newspapers and manuscripts therefore become inaccessible after a certain time.
  • liquid organic solvents in which the active substance to be supplied is dissolved;
  • the liquid solvents can be, for example, hydrocarbons, halogenated hydrocarbons such as chlorofluorocarbons, alcohols or their mixtures.
  • the substance can also be brought directly into the structure of the paper in the gaseous state as described in US-A- 3,969,549 and US-A- 3,771,958.
  • the present invention specifically relates to a paper product processing method, which requires no
  • the process for treating paper products with at least one active substance is characterized in that it comprises the following successive steps: 1 ° ) bringing the paper products into contact with a dense fluid at a temperature T- j and at a pressure Pj at least equal to the critical pressure P c of the fluid, this fluid being in the form of gas at ambient pressure and temperature and being relatively inert vis-à-vis paper products ;
  • the dense fluid is extracted.
  • the degradation products of the paper then in the second step, the structure of the paper, opened by this cleaning and swollen by the dense fluid, is impregnated with neutralizing and / or reinforcing principles.
  • the method further comprises at least one additional step consisting in bringing into contact, after the second step, the paper products i impregnated with a first active substance, with the fluid. dense at a temperature T3 and a pressure P3 at least equal to P c , the dense fluid containing another active substance than that used in the second step.
  • these stages of the process are carried out so as to obtain, at the end of the treatment, paper products having a pH of 7 to 8.5 so as not to degrade, by an excessively basic effect, the sizing of sheets of paper.
  • the following three stages of treatment with the dense fluid can be carried out:
  • This succession of steps can be repeated one or more times to improve the result on certain types of paper and allow better optimization of the neutralizing effect, therefore of the final pH.
  • the expression “dense fluid” means a fluid under a pressure P greater than the critical pressure P c of this fluid, which is preferably under temperature conditions T close to the critical temperature T c of the fluid, this temperature and this pressure being chosen to give the fluid a high extraction power v s vis-à-vis paper degradation products and a high dissolving or transporting power vis-à-vis La or active substances used.
  • This dense fluid can be chosen for example from carbon dioxide, sulfur hexafluoride, ammonia, saturated hydrocarbons, and nitrous oxide.
  • carbon dioxide is used because it is non-toxic, non-flammable, not very reactive and inexpensive. Furthermore, its supercritical conditions are very accessible since its critical pressure and temperature are 7.3MPa and 31 ° C respectively. According to the invention, the dense fluid can be in the subcritical or supercritical state.
  • subcritical fluid is meant a fluid at a temperature T lower than the critical temperature T c of the fluid, which in the process of the invention corresponds to the liquid state, since the pressure ( Pi P2 ' p 3-- » p ⁇ ⁇ of the fluid is always greater than the critical pressure P c .
  • supercritical fluid is understood to mean a fluid whose temperature T is greater than the critical temperature, which in the process of the invention corresponds to the superc ri ti state since the pressure p 1 p 2 ' p 3 --- p n of the fluid is always greater than the critical pressure.
  • the supercritical fluid in the state supercritical according to the invention corresponds to hatched area A.
  • the subcritical fluid in the liquid state corresponds to the hatched area B.
  • C0 2 exists in the form of gas in the area referenced C, in liquid form in the area referenced B ', and in solid form in the area referenced D.
  • a fluid is used under conditions of pressure (P ⁇ , P, p 3 or P n ) and of temperature (T ⁇
  • the pressure Pj, P 2 , P3 or P n can be chosen for example in the range from 6 to 50MPa, preferably 10 to 20MPa and better still 10-15MPa.
  • the temperature T-], T 2 , T3 or T n can be, for example, from 10 to 300 ° C, preferably from 20 to 100 ° C, and better still from 30 to 60 ° C.
  • all of the steps for bringing paper products into contact with the dense fluid under dynamic conditions are preferably carried out.
  • the pressure variation P can represent approximately 10% of Pj, P, P3 or P n over a period of 5 to 50 seconds.
  • This fluid can be easily removed at the end of treatment by lowering the pressure to bring it back to the gaseous state.
  • l In the dense state, l has a low viscosity, which makes it possible to reduce the energy expenditure necessary for setting it in motion, while benefiting from improved behavior in porous medium.
  • the invention requires no pretreatment and no finishing phase such as drying or elimination of the solvent, since the latter can be easily eliminated in gaseous form at ambient pressure and temperature at the end of treatment.
  • carbon dioxide when used, it is an apolar solvent which can promote the formation of hydrogen bridges between the cellulose fibers during the reinforcement process.
  • this solvent can be humidified in order to limit its drying effect on the paper.
  • the products treated by the process of the invention can therefore be directly recovered and then used at the end of the treatment.
  • the fluid used in the invention is chosen as a function of the active substances used and the products to be treated so as to have a high solvent power for these substances while being inert with respect to the products to be treated in order to do not degrade them.
  • Carbon dioxide C0 is advantageously used, in particular in the supercritical state.
  • the active substances used in the second step and in the possible additional steps can be of different types and depend in particular on the products to be treated and on their degree of degradation.
  • Substances capable of neutralizing the acidity of the papers, of strengthening their structure or of imparting other properties to them can be used. It is of course possible to use a mixture of various substances.
  • the active substances capable of neutralizing the acidity of the paper are in particular the organic carbonates of metals with Lca L i not er reux, for example The al ky L ca magnesium carbonates.
  • the noteworthy or similar alkali metal oxides such as magnesium oxide and zinc oxide, products known and currently used in solvent processes.
  • polymer type products such as, for example, polyvinyl butyric having above all a reinforcing effect.
  • the active ingredients of the "polymer” type can be transported and impregnated either directly or in the form of precursors (monomers for example) and polymerized in situ after impregnation.
  • the quantity impregnated must be well adjusted and very homogeneous in order to avoid overloads and therefore non-desirable polymerizations between sheets, for example. Dense fluids under pressure can promote these mechanisms by their adjustable solvent power, their low viscosity and their high diffusivity.
  • grains of very small diameter for example less than or equal to 10 nm, are preferably used to promote the reinforcing and neutralizing effects.
  • grafted silicas in particular with C0, is particularly advantageous since it is possible to obtain the neutralizing and reinforcing effect by creating hydrogen bridges.
  • the active substance When the active substance is not directly soluble in the dense fluid used, it can be dissolved in an auxiliary solvent which may or may not be soluble in the dense fluid.
  • heavy alcohols having at least 3 carbon atoms are used, for example isopropyl alcohol, since they are less penalizing for the other structures of books such as inks, than lighter alcohols.
  • the (the) substance (s) active (s) may be included in the fibrous or porous material to be treated, either by reacting di rect with this material, or through a suitable treatment which transforms in a form retained by the material to be treated, either by capi llarity or direct absorption in this material when the latter has a particular affinity for the active substance.
  • Treatments capable of modifying the active substance so that it is retained in the material to be treated can consist of a chemical or physicochemical treatment, leading for example to a soméri sati on, a polymerization or other reactions.
  • treatment can also be carried out at the end of the operation, after elimination of the dense fluid.
  • the invention also relates to an installation for implementing the method described above.
  • This installation includes:
  • the means for adding the (the) substance (s) active (s) to the dense fluid are constituted by a static switch (autoclave static load), an injector or a column in which circulate against the current the dense fluid and a Liquid phase comprising The (the) substan- this (s) active (s).
  • the installation further comprises means for bringing the treatment enclosure to atmospheric pressure by discharging the dense fluid and means for periodically varying the pressure of the dense fluid around P- j , P 2 , P 3 or P n .
  • the installation can also further comprise means for humidifying the dense fluid before it enters the enclosure, so as to limit its slight drying effect on the paper.
  • FIG. 1, already described, represents the state diagram of C0 2 .
  • FIG. 2 shows a processing installation to implement the method of L 'nvent i on.
  • this installation comprises a treatment enclosure (1) in which the materials to be treated (2) can be placed such as books.
  • the dense fluid containing or not containing the active substance or substances used for the treatment can be introduced into this enclosure (1) from a storage container (3) after having been brought to the pressure P desired by the compressor (5) and at the temperature T desired by the heat exchanger (7), then having been optionally charged with active substance (s) in the contactor (9) in which it is brought into contact static, by injection or against the current with the active substance introduced via line (11 ) and discharged through the pipe ( 13 ) .
  • the dense fluid containing the active substance (s) is introduced via the line (15) into the treatment enclosure ( 1 ) .
  • this fluid is recycled without pressure loss other than the pressure losses, at the inlet of the enclosure ( 1 ) via the line (17) the circulator ( 18 ) , the heat exchanger (7) and the contactor ( 9 ) where it is recharged with active substance.
  • the dense fluid leaving the treatment enclosure ( 1) is evacuated through the line ( 21 ) , then expanded by the expansion valve ( 23 ) and recycled into the storage container (3) after separation active substances (SA) in the separator ( 25 ) and cooling in the heat exchanger (27).
  • the recycling line ( 17 ) and the recirculator ( 18 ) are eliminated.
  • the dense fluid is then reintroduced into the enclosure (1) from the storage container (3) by means of the compressor ( 5 ) of the heat exchanger (7) and the contactor (9).
  • This treatment requires a C0 2 solvent level ranging from 1 to 100 kg of C0 / kg of treated product.
  • the compressor (5) is stopped and the treatment loop is decompressed by the expansion valve ( 23 ) as before.
  • the regulator (18) or of the valve (23) is ensured by appropriate regulation of the regulator (18) or of the valve (23), to have a treatment regime puL se.
  • the books are placed closed and stacked in the treatment enclosure (1) and a first treatment of the paper is carried out with C0 2 which is higher than at a pressure P j of 20 MPa and a temperature Ti of 40 ° C with a C0 rate corresponding to a total of 25kg of C0 2 per kg of pounds then a second the paper deacidification treatment using as active substance methylethyl magnesium carbonate (CMM) in C0 2 supercritical to a pressure P and a temperature T 2 identical to P and Tj.
  • CCMM methylethyl magnesium carbonate
  • the active substance ie methylethyl magnesium carbonate
  • a mixture of methanol and ethanol to form a 20% solution of carbonate.
  • Example 4 and 5 In these examples, the same procedure is followed as in Example 1, but silica grafted with an organic product is used as active substance and it is also introduced into the contactor (9). as a solution in ethanol.
  • Example 2 the same procedure is followed as in Example 1, but working at a lower pressure (13MPa) and at a temperature of 40 ° C. and not carrying out the first treatment step with CO alone.
  • Example 2 the same procedure is followed as in Example 1, but working at a lower pressure, 13 MPa and at a temperature of 40 ° C., in the two treatment stages.
  • This example shows one of the advantages of the invention which is the possibility of modulating by pressure the solvent power of the dense fluid so as to preserve the transportability of the active substance without this solvent power having a degrading effect on the book.
  • the extract obtained by supercritical C0 alone during the first stage is biphasic with:
  • Example 1 the same procedure is followed as in Example 1 for treating books having different types of paper, under the same pressure and temperature conditions as those of Examples 6 and 7, but with repetitions of the different steps. : - step 1 - extraction with C0 2 SC alone,
  • step 2 impregnation of the CI.M with C0 2 SC
  • step 3 identical to step 1
  • step 4 identical to step 2.

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  • Paper (AREA)
PCT/FR1992/000293 1991-04-04 1992-04-02 Procede et installation de traitement de produits en papier dans un fluide dense sous pression WO1992017640A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP92909511A EP0578736B1 (fr) 1991-04-04 1992-04-02 Procede et installation de traitement de produits en papier dans un fluide dense sous pression
DE69212467T DE69212467T2 (de) 1991-04-04 1992-04-02 Verfahren und anlage zur behandlung von papierprodukten mit flüssigkeiten grosser dichte
JP4508598A JP2987520B2 (ja) 1991-04-04 1992-04-02 圧力下、濃密流体中において紙製品を処理するプロセスおよび装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9104105A FR2674872A1 (fr) 1991-04-04 1991-04-04 Procede et installation de traitement de matieres fibreuses ou poreuses, notamment du papier, par un fluide dense sous pression.
FR91/04105 1991-04-04

Publications (1)

Publication Number Publication Date
WO1992017640A1 true WO1992017640A1 (fr) 1992-10-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR1992/000293 WO1992017640A1 (fr) 1991-04-04 1992-04-02 Procede et installation de traitement de produits en papier dans un fluide dense sous pression

Country Status (6)

Country Link
EP (1) EP0578736B1 (enrdf_load_stackoverflow)
JP (1) JP2987520B2 (enrdf_load_stackoverflow)
AT (1) ATE140742T1 (enrdf_load_stackoverflow)
DE (1) DE69212467T2 (enrdf_load_stackoverflow)
FR (1) FR2674872A1 (enrdf_load_stackoverflow)
WO (1) WO1992017640A1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018264A1 (en) * 1993-02-11 1994-08-18 Minnesota Mining And Manufacturing Company Methods of polymer impregnation
CN100421821C (zh) * 2000-08-22 2008-10-01 底古萨股份公司 利用压缩气体使载体基质被固体和/或液体化合物浸渍的方法和所得到的浸制材料

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2747697B1 (fr) * 1996-04-18 1998-06-26 Separex Sa Procede et installation de traitement de documents de papier par fluide a pression supercritique
DE10059494B4 (de) * 2000-11-30 2007-05-24 Zfb Project-Management Gmbh Konditionierungsmittel und Verfahren zur Konditionierung sowie dessen Verwendung
RU2243309C1 (ru) * 2003-11-17 2004-12-27 Федеральное государственное учреждение Российская национальная библиотека Способ нейтрализации кислотности бумаги

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676182A (en) * 1970-08-31 1972-07-11 Richard Daniel Smith Treatment of cellulosic materials
US3969549A (en) * 1974-12-24 1976-07-13 The United States Of America As Represented By The Librarian Of Congress Method of deacidifying paper
US4522843A (en) * 1984-01-25 1985-06-11 Kundrot Robert A Deacidification of library materials
EP0386436A2 (de) * 1989-02-11 1990-09-12 BATTELLE INGENIEURTECHNIK GmbH Rationelles Verfahren zur umweltfreundlichen Massenentsäuerung von Büchern und anderen Papiererzeugnissen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676182A (en) * 1970-08-31 1972-07-11 Richard Daniel Smith Treatment of cellulosic materials
US3969549A (en) * 1974-12-24 1976-07-13 The United States Of America As Represented By The Librarian Of Congress Method of deacidifying paper
US4522843A (en) * 1984-01-25 1985-06-11 Kundrot Robert A Deacidification of library materials
EP0386436A2 (de) * 1989-02-11 1990-09-12 BATTELLE INGENIEURTECHNIK GmbH Rationelles Verfahren zur umweltfreundlichen Massenentsäuerung von Büchern und anderen Papiererzeugnissen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994018264A1 (en) * 1993-02-11 1994-08-18 Minnesota Mining And Manufacturing Company Methods of polymer impregnation
US5508060A (en) * 1993-02-11 1996-04-16 Minnesota Mining And Manufacturing Company Method of polymer impregnation
JP3263080B2 (ja) 1993-02-11 2002-03-04 ミネソタ マイニング アンド マニュファクチャリング カンパニー ポリマーの含浸法
CN100421821C (zh) * 2000-08-22 2008-10-01 底古萨股份公司 利用压缩气体使载体基质被固体和/或液体化合物浸渍的方法和所得到的浸制材料

Also Published As

Publication number Publication date
JP2987520B2 (ja) 1999-12-06
DE69212467T2 (de) 1997-02-06
EP0578736A1 (fr) 1994-01-19
EP0578736B1 (fr) 1996-07-24
DE69212467D1 (de) 1996-08-29
FR2674872A1 (fr) 1992-10-09
JPH06506270A (ja) 1994-07-14
ATE140742T1 (de) 1996-08-15
FR2674872B1 (enrdf_load_stackoverflow) 1997-02-07

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