EP0578736B1 - 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
EP0578736B1
EP0578736B1 EP92909511A EP92909511A EP0578736B1 EP 0578736 B1 EP0578736 B1 EP 0578736B1 EP 92909511 A EP92909511 A EP 92909511A EP 92909511 A EP92909511 A EP 92909511A EP 0578736 B1 EP0578736 B1 EP 0578736B1
Authority
EP
European Patent Office
Prior art keywords
dense fluid
process according
pressure
treatment
active substance
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.)
Expired - Lifetime
Application number
EP92909511A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0578736A1 (fr
Inventor
Maurice Carles
Alain Gouchet
Christian Perre
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
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Publication date
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Publication of EP0578736A1 publication Critical patent/EP0578736A1/fr
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Publication of EP0578736B1 publication Critical patent/EP0578736B1/fr
Anticipated expiration legal-status Critical
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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 especially papers manufactured industrially from wood, undergo damage over time which is due in particular to the degradation of the cellulose molecules by hydrolysis and / or oxidation reactions, 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.
  • paper documents that have undergone such degradation can be processed to make them reusable.
  • These treatments consist in bringing into the structure of the paper agents neutralizing the acidity or other appropriate chemical substances making it possible to restore the properties of the paper.
  • 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 subject of the present invention is precisely a process for the treatment of paper products, which does not require any pre-treatment or post-treatment of the treated papers, which does not pose any problem of solvent and which does not otherwise penalize the structure of the documents treated.
  • the degradation products of the paper are thus extracted in the first step by the dense fluid, then the structure of the paper, impregnated by this cleaning and swollen by the dense fluid, neutralizing and / or reinforcing active ingredients.
  • the method further comprises at least one additional step consisting in bringing the paper products impregnated with a first active substance into contact with the dense fluid at a temperature after the second step. T 3 and a pressure P 3 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 surface bonding of paper sheets.
  • 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 at 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 vis-à-vis paper degradation products and a high dissolving or transport power vis-à-vis the active substance or 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.
  • 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 Tc of the fluid, which in the process of the invention corresponds to the liquid state, since the pressure (P 1 , P 2 , P 3 . ..P n ) of the fluid is always higher than the critical pressure P c .
  • supercritical fluid is meant a fluid whose temperature T is higher than the critical temperature, which in the process of the invention corresponds to the supercritical state since the pressure P 1 , P 2 , P 3 ... P n fluid is always above 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.
  • CO 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.
  • the density of molecules of the fluid and therefore the solvent power of the fluid can be adjusted with respect to the degradation products of the paper and the active substances used. .
  • a fluid is used under conditions of pressure (P 1 , P 2 , P 3 or P n ) and temperature (T 1 , T 2 , T 3 or T n ) sufficient on the one hand, to give it a certain density of molecules allowing a sufficient dissolving power or transportability and, on the other hand, to optimize this solvent power and this transportability so that it is not penalizing vis-à-vis paper products, in particular with regard to ink and treated bindings.
  • the pressure P 1 , P 2 , P 3 or P n can be chosen for example in the range from 6 to 50 MPa, preferably 10 to 20 MPa and better still 10-15 MPa.
  • the temperature T 1 , T 2 , T 3 or T n may for example be from 10 to 300 ° C, preferably from 20 to 100 ° C, and better still from 30 to 60 ° C.
  • all the stages of bringing paper products into contact with the dense fluid under dynamic conditions are preferably carried out.
  • one uses in each step 1 to 100 kg of dense fluid per kg of products to be treated.
  • the pressure variation P can represent approximately 10% of P 1 , P 2 , P 3 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 return it to the gaseous state.
  • the process of 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. Furthermore, this solvent can be moistened 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 according to 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 so as not to degrade them. .
  • Carbon dioxide CO 2 is advantageously used, especially 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 their degree of degradation. Substances capable of neutralizing the acidity of the papers, of strengthening their structure or of giving them other properties 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 organic carbonates of alkaline earth metals, for example magnesium alkylcarbonates, oxides of alkaline earth metals or the like such as magnesium oxide and zinc oxide, products known and currently used in solvent processes.
  • the active ingredients of the "polymer” type can be transported and impregnated either directly or in the form of precursors (eg monomers) and polymerized in situ after impregnation.
  • the quantity impregnated must be well adjusted and very homogeneous in order to avoid overloads and therefore undesirable 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 CO 2 , 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 the books such as inks, than the lighter alcohols.
  • auxiliary solvent When using such an auxiliary solvent, one can no longer speak of direct solubility of the active substance in the dense fluid, but of indirect solubility or of transportability of the active substance and its solvent by the dense fluid under pressure.
  • the solvent contains the active substance and the whole is dissolved or transported by the dense fluid under pressure.
  • the active substance (s) can be included in the fibrous or porous material to be treated, either by direct reaction with this material, or by means of an appropriate treatment which transforms it into a form retained by the material to be treated, either by capillarity or direct absorption in this material when the latter has a particular affinity for the active substance.
  • Treatments capable of modifying the active substance for it to be retained in the material to be treated may consist of a chemical or physicochemical treatment, leading for example to isomerization, polymerization or other reactions.
  • treatments include chemical or photochemical treatments, irradiation, heat treatments, etc.
  • This treatment can also be carried out at the end of the operation, after elimination of the dense fluid.
  • the means for adding the active substance (s) to the dense fluid consist of a static contactor (autoclave with static charge), an injector or a column in which the dense fluid circulates against the current and a liquid phase comprising the substance (s) active.
  • the installation further comprises means for bringing the treatment enclosure to atmospheric pressure by evacuating the dense fluid and means for periodically varying the pressure of the dense fluid around P 1 , 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.
  • 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 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 possibly been loaded with active substance (s) in the contactor (9) in which it is brought into contact in static, by injection or counter-current with the active substance introduced via line (11) and discharged through the pipe (13).
  • the dense fluid containing the active substance or substances is introduced via the line (15) into the treatment enclosure (1).
  • this fluid is recycled without loss of pressure 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 via the pipe (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 pipe (17) and the recirculator (18) are eliminated.
  • the dense fluid is recycled via the valve (23) in the storage container (3) by adjusting this valve to maintain the treatment pressure at the desired value.
  • the dense fluid is then reintroduced into the enclosure (1) from the storage container (3) via the compressor (5) of the heat exchanger (7) and the contactor (9).
  • This treatment requires a CO 2 solvent level ranging from 1 to 100 kg of CO 2 / kg of treated product.
  • the compressor (5) is stopped and the treatment loop is decompressed by the expansion valve (23) as before.
  • the books are placed closed and stacked in the treatment enclosure (1) and a first treatment of the paper is carried out with supercritical CO 2 at a pressure P 1 of 20 MPa and a temperature T 1 of 40 ° C with a CO 2 level corresponding to a total of 25 kg of CO 2 per kg of pounds, then a second the paper deacidification treatment using as active substance methylethyl magnesium carbonate (CMM) in supercritical CO 2 at a pressure P 2 and a temperature T 2 identical to P 1 and T 1 .
  • CCM methylethyl magnesium carbonate
  • the active substance that is to say methylethyl magnesium carbonate, is dissolved beforehand in a mixture of methanol and ethanol to form a 20% solution of carbonate.
  • This solution is introduced into the contactor (9) where it dissolves in the supercritical CO 2 to form supercritical CO 2 containing about 1% by weight of methylethyl magnesium carbonate solution.
  • a dense fluid rate of 30 kg / kg of product the pH of the paper is measured and the alkaline reserve formed is evaluated (in meq of acid necessary to neutralize the paper).
  • Example 2 the same procedure is followed as in Example 1, but another batch of books of different paper nature is used whose pH before treatment is different. The results obtained are also given in the attached table.
  • silica grafted with an organic product is used as active substance and it is introduced into the contactor (9) also in the form of 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 performing the first step of treatment with CO 2 alone. .
  • 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., 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.

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  • Paper (AREA)
EP92909511A 1991-04-04 1992-04-02 Procede et installation de traitement de produits en papier dans un fluide dense sous pression Expired - Lifetime EP0578736B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9104105 1991-04-04
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.
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

Publications (2)

Publication Number Publication Date
EP0578736A1 EP0578736A1 (fr) 1994-01-19
EP0578736B1 true EP0578736B1 (fr) 1996-07-24

Family

ID=9411474

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92909511A Expired - Lifetime EP0578736B1 (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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2243309C1 (ru) * 2003-11-17 2004-12-27 Федеральное государственное учреждение Российская национальная библиотека Способ нейтрализации кислотности бумаги

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5340614A (en) * 1993-02-11 1994-08-23 Minnesota Mining And Manufacturing Company Methods of polymer impregnation
FR2747697B1 (fr) * 1996-04-18 1998-06-26 Separex Sa Procede et installation de traitement de documents de papier par fluide a pression supercritique
DE10041003A1 (de) * 2000-08-22 2002-03-28 Sueddeutsche Kalkstickstoff Verfahren zum Imprägnieren einer Trägermatrix mit festen und/oder flüssigen Verbindungen mit Hilfe komprimierter Gase und so imprägnierte Stoffe
DE10059494B4 (de) * 2000-11-30 2007-05-24 Zfb Project-Management Gmbh Konditionierungsmittel und Verfahren zur Konditionierung sowie dessen Verwendung

Family Cites Families (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
DE3904111A1 (de) * 1989-02-11 1990-08-16 Battelle Institut E V Verfahren und vorrichtung zur umweltfreundlichen massenentsaeuerung von buechern und anderen papiererzeugnissen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2243309C1 (ru) * 2003-11-17 2004-12-27 Федеральное государственное учреждение Российская национальная библиотека Способ нейтрализации кислотности бумаги

Also Published As

Publication number Publication date
JP2987520B2 (ja) 1999-12-06
DE69212467T2 (de) 1997-02-06
EP0578736A1 (fr) 1994-01-19
DE69212467D1 (de) 1996-08-29
FR2674872A1 (fr) 1992-10-09
JPH06506270A (ja) 1994-07-14
ATE140742T1 (de) 1996-08-15
WO1992017640A1 (fr) 1992-10-15
FR2674872B1 (enrdf_load_stackoverflow) 1997-02-07

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