EP1060220B1 - Deacidification treatment of printed cellulosic materials - Google Patents
Deacidification treatment of printed cellulosic materials Download PDFInfo
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- EP1060220B1 EP1060220B1 EP99901377A EP99901377A EP1060220B1 EP 1060220 B1 EP1060220 B1 EP 1060220B1 EP 99901377 A EP99901377 A EP 99901377A EP 99901377 A EP99901377 A EP 99901377A EP 1060220 B1 EP1060220 B1 EP 1060220B1
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- alcohol
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
Definitions
- the present invention relates generally to compositions and methods for deacidification treatment and preservation of printed cellulosic materials, such as books, manuscripts and other image and information bearing documents and publications and works of art on paper, which may deteriorate or which may have become deteriorated through aging.
- Moisture variation in anhydrous raw materials presents a significant problem when using most known treatment methods.
- either powder or gel precipitates will be formed, depending on time, reactivity, temperature and pressure conditions. These precipitates may prevent (poison), impede (slow) a manufacture or reaction rate and detrimentally affect the deacidification workability of solutions (clog paper substrates).
- the precipitates also may deposit on and deface books and documents and block or clog filters, pipes, valves and other restricted passages in processing equipment. They may also deposit thick coatings on walls of tanks and, depending on relative densities, separate into top or bottom phase composition layers or even, in extreme cases, actually turn the treating solution (initially thinner than water) into an immobile gelatin-like gel.
- ultra-low moisture alcohol and aliphatic hydrocarbon solvents are not available commercially in standard containers, e.g., in 19 litre (5-gallon) pails or 208 litre (55-gallon) drums.
- Industrial solvent manufacturers do not deliver their solvents in an ultra-dry condition, i.e., below 15 or 25 ppm.
- the maximum moisture content specification for a 208 litre (55-gallon) drum of research grade "anhydrous" methanol from Fisher Scientific is 1,000 ppm.
- Sub-Micrometer (less than 0.2 micrometer) coal black particles are known to precipitate in concentrates prepared for current treatment methods.
- the particles may be introduced as trace heavy metal (iron, cobalt, copper, etc.) . impurities in the metals reacted with alcohols to produce alkoxide powders for use in treatment or by external conditions. These particles contaminate and discolor the treatment concentrate and must be removed before use in preservation. Additionally, allowing the particles to agglomerate naturally then filtering through a 0.2 micron absolute membrane filter limits the concentration of treatment concentrates that can be manufactured. For example, concentrations of organic magnesium of up to only 25 percent by weight in methanol are a maximum.
- the more alkaline pH values produced by organic magnesium carbonate treatments may cause undesirable color changes. These treatments may cause sensitive inks, pigments, and dyes to change color when the cellulosic material is changed from a deteriorating acidic condition to a stable alkaline condition.
- the present invention provides a composition for deacidifying a printed cellulosic material comprising in solution: 0.1 - 4 wt.% of at least one of an organic magnesium carbonate, an organic aluminium carbonate and an organic zinc carbonate; 0 - 10 wt.% of a C 1 - C 4 alcohol having a moisture content of less than 100 ppm; and 86 - 99 wt.% of a solvent having a moisture content of less than 100 ppm comprising an aliphatic hydrocarbon and/or a hydrofluorocarbon.
- the present invention provides a process for making a composition for deacidifying printed cellulosic materials comprising: treating a C 1 - C 4 alcohol with a molecular sieve or other desiccant to reduce the moisture content thereof below 100 ppm to produce an ultra-low moisture alcohol; adding carbon dioxide and a metal in the form of metal chips or a metal alkoxide, the metal being selected from aluminium, magnesium or zinc, to the ultra-low moisture alcohol to form an organic metal carbonate composition and submicron-sized, magnetically susceptible impurities; magnetically removing the submicron-sized magnetic impurities from the composition; filtering the resulting organic metal carbonate composition through a submicrometer filter to produce a deacidification treatment concentrate; and blending the deacidification treatment concentrate with additional solvent having a moisture content of less than 100 ppm comprising an aliphatic hydrocarbon and/or a hydrofluorocarbon to prepare the deacidifying composition.
- the ultra-dry solvents which generally are available in standard volume commercial containers, are made in a process comprising passing the solvent through one or more drying columns. The solvent then is recirculated to the container, with re-circulation of the solvent through the container and column occurring for a period effective for reducing the moisture content to less than about 100 ppm to provide an ultra-dry solvent.
- metal or “metal agent” means organic aluminum, magnesium, zinc or blends thereof.
- metal alkoxide means an organic aluminum alkoxide, magnesium alkoxide, zinc alkoxide or blends thereof.
- metal carbonate means an organic aluminum carbonate, magnesium carbonate, zinc carbonate or blends thereof.
- the present invention is directed to a composition and method for treating printed cellulosic materials to preserve the materials with little to no negative impact on inks, images, bindings or other features.
- the invention also is directed to methods of making the composition. More particularly, the invention is directed to compositions including organic aluminum, magnesium, and/or zinc agents and ultra-dry solvents.
- the metal agents are blended with ultra-dry alcohol solvents with carbon dioxide to produce a non-aqueous deacidification concentrate composition.
- This concentrate composition is blended with ultra-dry solvents to produce a deacidification composition that can be used in sprays and solutions to protect books and documents against aging.
- metals 10 first are blended with an ultra-dry solvent 12 and carbon dioxide 14.
- the metals used in the composition are organic aluminum, magnesium, zinc or combinations thereof.
- the metal may be in the form of metal chips or a metal alkoxide.
- the solvent is an alcohol having 1 to 4 carbon atoms.
- the metal and solvent may be blended with stirring, shaking or other agitation as necessary to provide a blend composition.
- the metal, ultra-dry solvent and carbon dioxide react to provide a deacidification agent 16 comprising metal carbonate.
- Magnets 18 are immersed or otherwise contacted with the deacidification agent for removal of sub-micron particle impurities to provide a deacidification agent intermediate composition 20.
- the organic metal carbonate concentrates are refined and purified by removing iron and associated heavy metals (e.g. copper and cobalt) present in the black magnetic particles.
- the submicrometer particles are removed by attachment to magnets, agglomeration and filtration through membrane filters. Additionally, allowing the agglomerates to settle and decanting the concentrate may be used, as well as any combination of these procedures.
- Magnetic filtration may occur in single step (FIG. 1) or multiple step magnetic filtration (not shown).
- the primary advantages of a single step procedure are speed of removal and minimization of the contamination from moisture. Additionally, the resulting concentrates are thinner and filter rapidly, subsequent blending, mixing, and transfer processes occur more readily, and costs of more processing and losses of concentrate composition during additional membrane filtration steps are avoided.
- Single step magnetic filtration emphasizes attracting particles to the magnetic poles. Though higher concentrations are possible, typically 25.0, 37.5, 50.0, 62.5, or 75.0 percent concentrations in methanol are manufactured. Concentrations in ethanol and isopropanol are typically 25.0 to 37.5 percent by weight. Magnets are immersed in the completed concentrate to agglomerate, attract, and collect the particles.
- Teflon coated rod (ALNICO V) magnets 13 mm x 150 mm (1/2" by 6") designed for use as spin bars in magnetic mixers may be used.
- Other magnets including electromagnets, magnetic grids, or magnetic particles which can readily be separated from the solutions being treated, and flow-through magnetic treatment chambers, may be substituted for the spin bar magnets.
- the magnets may be placed either in or outside of the concentrate solution being magnetically filtered.
- Multiple step filtration involves repeating the complete single step cycle at two or more pre-selected concentrations.
- the organic metal - carbonate concentrate is initially manufactured to 37.5 percent by weight concentration, magnetically filtration treated, and membrane filtered through a 0.2 micron filter. Then 25 percent more organic metal carbonate is blended with the concentrate and the now 62.5 percent concentrate is again magnetically and membrane filtered. Finally, 12.5 percent more organic metal carbonate is blended in, magnetically and membrane filtered to produce a concentration level of 75.0 percent by weight in methanol.
- the primary advantages of the multi-step procedure are that stronger concentrates exceeding 100 percent by weight can be produced, and the quantities of fine black particulates do not build up because they are removed as they are formed.
- the potential for alcohols from multi-step concentrates to deface books and documents by dissolving inks is essentially eliminated.
- the quantity of free alcohol is very low, typically below 1 percent, and preferably below 0.5 percent by weight in the paper treating solutions.
- the composition is filtered 22 using membrane filtration.
- Sub-micron pleated membrane (0.2 micrometer or smaller pore size) filtration occurs after the desired concentration is attained, typically at the 37.5 and 62.5 percent concentrations, and after the solution has been separated from the magnets bearing the black magnetic particles.
- the 25.0 percent by weight organic metal carbonate concentrations can be filtered through a 0.2 micrometer filter after overnight treatment, the 37.5 percent concentrate two days after manufacture.
- the concentrates may be subjected to moderate warming during their manufacture. Additional amounts of ultra-dry solvents may be blended with the concentrates, as necessary for filtration. Filtration below the boiling point of the alcohol being used is essential. The heat reduces the viscosity of the concentrates, and improves magnetic filtration by reducing the required propelling pressure and increasing the rate of flow through membrane filters.
- Membrane filters commercially available having pores larger than 0.2-microns do not completely remove the agglomerated particles and residual fines from concentrate solutions.
- Ultra fine membrane filters e.g., 0.1, 0.05, and 0.01-micron actual pore size (finest currently commercially available is 0.01-microns) may be substituted for the 0.2 micrometer filters to produce more pure filtrates.
- Filtration provides a deacidification concentrate 24.
- the deacidification concentrate then is blended with an ultra-dry solvent 26 to provide a deacidification composition 28.
- the solvent is an alcohol with 1 to 4 carbon atoms, an aliphatic hydrocarbon with 1 to 8 carbon atoms, a fluorocarbon hydrocarbon, or mixtures thereof.
- the deacidification concentrate and solvent may be blended with stirring, shaking or other agitation as necessary to provide a blend composition.
- organic aluminum alkoxides with or without a carbon dioxide adduct and either alone or in combination with organic magnesium or zinc agents, are also useful deacidification agents. They may be soluble directly in aliphatic and fluorocarbon solvents without an alcohol cosolvent.
- the commercially available solvents that may be used in the present invention include alcohols having 1 to 4 carbon atoms and aliphatic and halogenated hydrocarbon solvents.
- Such solvents include methanol, ethanol, isopropanol, isobutanol, propane, butanes, pentanes, isohexanes, heptanes, difluoroethane (HFC-152a), and tetrafluoroethane (HFC-134a), HFC-32, HFE-7100, HFE-7200, and HFC-10-43MEE.
- Moisture which may be present in solvents presents a major problem in preparing stable and non defacing organic metal carbonate deacidification compositions, sprays, and solutions. Moisture, even under 50 or 100 ppm, may react with organic metal carbonates to form soluble hydrates or gels that may thicken the solution or produce precipitates.
- the moisture level of alcohol solvents is no more than about 100 ppm and in a very important aspect, no more than about 25-50 ppm.
- the moisture level of fluorocarbon and aliphatic solvents is no more than about 100 ppm and in a very important aspect, no more than about 5-15 ppm.
- the composition of the invention comprises fluorocarbon solvents.
- the fluorocarbon solvent is HFC-134a.
- Mass deacidification solutions containing HFC-134a solvent have almost no detrimental effect on all printing inks tested.
- Higher alkaline reserves are possible, if desired, because the metal carbonates, especially MMMC concentrates, have increased solubility in HFC-134a. It is possible to achieve increased concentrate solubility using fluorocarbon solvents in the composition of the present invention, as compared to chlorofluorocarbon solvents.
- Previously soluble inks such as purple mimeograph, photocopy, and fast printing, offset inks that HCFC solvents such as HCFC-22 destroyed, are unaffected by treatment with HFC-134a or HFC-152a, with the same and far higher levels of alcohol.
- Solvents in the mass deacidification composition of the present invention can be completely recovered and recycled indefinitely with minimal benefaction requirements beyond adjustment for additional alcohol introduced in the make-up concentrate.
- Solids contents from about 25 to about 110 percent by weight of the organic metal carbonate in methanol may readily be produced, from about 25 to about 50 percent in ethanol, from about zero to about 40 percent in isopropanol and from about 0 to about 30 percent is isobutanol.
- HFC-152a difluoroethane
- HFC-134a tetrafluoroethane
- the concentrates may instantaneously precipitate out of solution on contact with HFC-134a and slowly, over one to three or more days, gradually with agitation (shaking and stirring) form a stable solution.
- the concentrates tend to go into solution in HFC-134a very rapidly when the HFC-134a is added in increments, e.g., 1:1, 1:4, 1:8, etc.; whereas direct blending at a 1:8 ratio produces a precipitate.
- a preferred deacidification composition for preserving paper includes from about 0.1 to about 4.0 percent of organic metal carbonate, from about 0.5 to about 10 percent by weight of ultra-dry alcohol and from about 86 to about 99 by weight aliphatic or fluorocarbon solvent, each based upon the weight of the total composition. In an important aspect, from about 0.5 to about 3.0 percent metal carbonate of the deacidification composition is thoroughly impregnated throughout the paper being protected against aging.
- One deacidification composition comprises methoxy magnesium methyl carbonate (MMMC) deacidification agent (which may include ethoxy components) blended with HFC-134a at 0.5 to 4.0% by weight with a very low level, less than 1% by weight, of free methanol in the treatment composition. More methanol up to 10 percent may be used, if desired.
- MMMC methoxy magnesium methyl carbonate
- a second composition comprises from about 0.25 to about 5.0 percent by weight of isopropoxy magnesium isopropyl carbonate (PMPC) blended with HFC-134a solvent including from about 1.0% to about 10% isopropanol.
- the PMPC concentrate may include methyl and/or ethyl carbonate components.
- MMMC and PMPC produce similar deacidification treatment results with HFC-134a.
- the MMMC is preferred because stronger concentrates may be prepared, the recovered solvents are easier to recycle, the treated books have a much lower odor level immediately after treatment and hazards are reduced because less flammable material is involved.
- Solutions of PMPC concentrate in aliphatic hydrocarbon solvents are extremely stable and combinations of solvents even dry to powder in open beakers in air without precipitation.
- Non-clogging aerosol sprays, solutions for brushing, and dipping paper may be prepared that do not produce white deposits during treatment.
- Ultra-drying in accordance with the present invention provides more stable deacidification products during shipment, storage, and use, as well as allows manufacture of products not possible until now.
- the compositions of the present invention are further blended with ultra-dried solvents to produce non-aqueous deacidification compositions for use as sprays and solutions for preserving books and documents.
- ultra-drying of the solvents With ultra-drying of the solvents, the quality and purity of starting solvents are established to a standard condition and can be used to produce finished products with predictable and reproducible properties.
- Solvents which are delivered in standard 208 litre (55-gallon) drums or similar containers, typically having moisture levels of at least about 1000 ppm, may be inexpensively transformed into ultra-dry solvents using the apparatus of the present invention, as shown in FIG. 2.
- the drums 50 have two threaded openings (one 5 cm (2") I.D. opening 51 and one 2 cm (3/4") I.D. opening 61).
- a dip tube 52 or similar piping extends into the drum through the 5 cm. I.D. opening 51, preferably down to at or near the bottom of the drum.
- One or more pumps 56 draw the solvent from the drum 50 up through the dip tube 52 and through the inlet line 54 to one or more drying columns 58.
- the solvent is passed through the columns and returned back to the drum via a return line 60.
- the return line extends through the 2 cm I.D. opening 61.
- the returned solvent is discharged via a tube 62.
- the tube 62 is angled or otherwise configured to promote splashing and circulation as the solvent is discharged in order to provide a mixing action.
- the solvent is recirculated through the drum and column until the moisture content is reduced to the desired level to provide an ultra-dry solvent.
- the solvent may be removed via a removal line 68 and transferred into smaller containers, such as 25 litre (6.5 gallon) carboys, for subsequent use, if desired.
- a source 64 of nitrogen gas, or equivalent, is connected to the headspace in the drum to provide an inert atmosphere and a pressure head for pumping. Valves 66 control the flow of gas into the drum.
- valves 72 control the flow through the drum and columns.
- Sight valves 74 are provided along the lines, as necessary.
- the preferred materials for transfer hoses, connections, and valves are Teflon and stainless steel. For safety's sake, equipment and hoses must be grounded because the flowing solvents can produce static electric charges that, if not discharged, may cause electric sparks.
- UOP Molecular Sieve M/S 3A is effective in drying methanol, ethanol, and isopropanol; HFC and aliphatic hydrocarbon solvents.
- UOP Molecular Sieve M/S 4A, XH-7, and XH-9 may be used to dry and also remove alcohol from HFC, and aliphatic hydrocarbon solvents.
- Alternative drying products include highly desiccated silica gel and desiccant aluminum oxide and silicate powders. All of these desiccants may be used in alternate forms; e.g., molded core dryers prepared to fit into a specific steel shell. Fluorocarbon solvents, such as HFC-134a, may cause some of these desiccants, e.g., UOP M/S 3A, to evolve a fine, white powder that can be removed during filtration.
- both lines extend through the same opening of the drum.
- the inlet line 54 and return line 60 both extend through the 5 cm I.D. opening 51.
- the removal line 80 extends from the return line 60 above the drum. The remaining features are as shown and described above for FIG. 2.
- the deacidification compositions of the present invention may be used in processes for treating and preserving printed cellulosic materials.
- the compositions can be used to prepare aerosols, solutions or other forms, as desired.
- the deacidification compositions may be used with any known treatment process.
- a process for mass deacidification using the composition in a solution form includes first thoroughly drying under vacuum the materials to be treated. The materials then are contacted with the composition for a period of time effective for thoroughly wetting the materials. During contact, the composition may be impregnated under pressure into the materials. After the solution is removed from the materials, any solution remaining in the materials is vaporized for recovery and recycling under vacuum conditions. In this process, it is possible to recover at least about 93-95 % of the deacidification solution, which can be re-used in the process.
- Anhydrous methanol delivered in a 200 liter drum is treated using the apparatus of FIG. 1.
- the methanol initially contains 900 ppm water.
- the drying columns are 61 cm (24") high columns filled with UOP molecular sieve desiccant M/S 3A., connected by 1/4" I.D. tubing Circulation through Column 1 and subsequently Column 2 is continued for 36 hours consecutively in each drying column.
- the final water content of the methanol after treatment is 25 ppm.
- a 208 litre (55-gallon) drum of isopropanol is ultra-dried as described in Example 1.
- the moisture content of the isopropanol is reduced from 800 ppm at beginning to 20 ppm at end.
- Isopentane solvent is treated in a 208 litre (55 gallon) stainless steel drum with the apparatus of FIG. 3.
- the moisture content of the isopentanes solvent is reduced from 1,000 ppm at beginning to 15 ppm at end.
- Example 2 On Day 1, four kilograms of granulated magnesium ethoxide and carbon dioxide gas are added to two 25 litre (6.5-gallon) flint glass carboy containing 14 liters of ultra-dry methanol prepared in Example 1. The components are reacted to produce a coal black, organic magnesium carbonate solution of MMMC in methanol.
- the magnesium ethoxide is kept in suspension in the methanol using an electromagnetic mixer; the carbon dioxide gas is added at ambient pressure at a rate of 0.14 m 3 /hr. (5 subic feet per hour) through a gas diffusion stone.
- the four magnets are removed and the mother liquor, now a translucent gray color, is filtered using 100 kPa (15 psig) nitrogen gas pressure through a 50 cm (20") long, 0.2-micron membrane filter in fifteen minutes to produce a water clear, light straw colored concentrate solution of filtrate.
- the poles of the magnets were coated with a fine black powder 1.6 mm to 3.2 mm (1/16" to 1/8") thick when removed from the concentrate.
- the mother liquor without magnetic filtration in the second concentrate solution is still coal black. It has a hazy, blackish gray amber color after being filtered through a 0.2-micrometer filter. Most of the black particles remain so small they pass through the 0.2-micrometer pores.
- Example 4 On Day 1, three kilograms of granulated magnesium ethoxide and carbon dioxide gas are added to two 25 litre (6.5-gallon) flint glass carboys containing 15 liters of ultra-dry isopropanol prepared in Example 2, and reacted as described in Example 4 to form isopropoxy magnesium isopropyl carbonate (PMPC). On completion of the reaction, magnets are inserted in one carboy to provide magnetic filtering, and the concentrates are maintained at 43°C (110°F) as described in Example 4.
- PMPC isopropoxy magnesium isopropyl carbonate
- the mother liquor remains black and, after filtering through a 0.2-micron filter, is a blackish charcoal gray color.
- the PMPC concentrate Without magnetic filtration and concentrate heating, the PMPC concentrate needs weeks of natural aging for agglomeration before it can be filtered to a dark amber concentrate.
- MMMC MMMC
- a 37.5 percent concentrate of MMMC is prepared and magnetically filtered as described in Example 5. Also on Day 3, four kilograms more granulated magnesium ethoxide and carbon dioxide gas are reacted with the filtrate to produce a 62.5 percent, coal black MMMC concentrate. Again four magnets are inserted to provide magnetic filtration, and the concentrate is maintained at 43°C (110° F).
- the four magnets are removed, cleaned, dried, and replaced. Their poles are coated with a fine black powder 1.6 mm to 3.2 mm (1/16" to 1/8") thick when removed from the concentrate.
- the four cleaned magnets are re-inserted on Day 5, and contents kept at 43°C (110°F).
- the magnets (coated 1/16" to 1/8" thick) are again removed; and the 62.5 percent concentrate is filtered for the first time with a 140 kPa (20 psig) Nitrogen gas pressure through a 0.2 micrometer filter in 45 minutes.
- the concentrate filtrate is a light amber color that dries to a snow white powder.
- the PMPC solution initially hazy from fine bubbles, clears to give a crystal clear, water white solution in the sight glasses with no signs of discoloration, precipitation, or phase separation before and after use, as compared to HCFC-22 solution and previous CFC containing solutions which show a slight yellowing after use.
- Example 4 MMMC concentrate 13 kg ((28.5-pounds))from Example 4 is diluted with 26 kg (57-pounds) of HFC-134a in a 60 litre (16-gallon) tank and mixed for 15 minutes on a seesaw shaker. 26 more kg (Fifty-seven pounds) of HFC-134a are added, and mixed again for 15 minutes to form a 1:5 ratio solution.
- the actual mass deacidification solution is prepared in clean, vacuum dried 47 litre (12.5-gallon) steel cylinders in four weighing and two mixing steps: (1) 12 kg (26 lbs) of HFC-134a Recovered Solvent; (2) 10.8 kg (23.75 lbs.) MMMC at 1:5 Ratio; (3) 11 kg (25 lbs.) HFC-134a Recovered Solvent; (3a) Mix on Seesaw Shaker for 10 minutes; (4) 22.8 kg (50.25 lbs.) HFC-134a Recovered Solvent; (4a) Mix on Seesaw Shaker for 15 minutes.
- the results equal or exceed the quality of treatments from all previous treatments including the PMPC/HFC-134a treatment of Example 9.
- the MMMC/HFC-134a solution treatment is preferred because it has less residual odor, is easier to manufacture and filter, is more readily recovered and recycled, and its stronger concentrates produce higher alkaline reserves.
- MZMC concentrate 13 kg ((28.5-pounds)) from Example 6 is diluted with 26 kg (57-pounds) of HFC-134a in a 60 litre (16-gallon) tank and mixed for 15 minutes on a seesaw shaker. 26 more kg (Fifty-seven pounds) of HFC-134a are added, and mixed again for 15 minutes to form a 1:5 ratio solution.
- the actual mass deacidification solution is prepared in clean, vacuum dried 47 litre (12.5-gallon) steel cylinders in four weighing and two mixing steps: (1) 12 kg (26 lbs.) HFC-134a Recovered Solvent; (2) 10.8 kg (23.75 lbs.) MZMC 1:5 Ratio; (3) 11 kg (25 lbs.) HFC-134a Recovered Solvent; (3a) Mix on Seesaw Shaker for 10 minutes; (4) 22.8 kg (50.25 lbs.) HFC-134a Recovered Solvent; (4a) Mix on Seesaw Shaker for 15 minutes.
- Example 4 (2) 1.8 kg (4.0 lbs.) PMPC/HFC-134a (1:1 ratio) (Example 7); (3) 6.8 kg (15.0 lbs.) Ultra-dry HCFC-141b (Example 4); (4) 0.9 kg (2.0 lbs.) HFC-134a; (4a) Nitrogen gas at 55 kPa (80 psig); (4b) Mixing on Seesaw Shaker for 10 min.
- a 17 litre (4.5-gallon) cylinder of Soft Spray is prepared as is described in Example 11 except flammable solvents are substituted for HCFC-141B and HFC-134a: (1) 0.45 kg (1.00 lbs) Ultra-Dry Isopropanol (Example 3); (2) 4.5 kg (10.00 lbs). Ultra-dry Low aromatic heptanes (Example 4); (3) 1 kg (2.125 lbs.) PMPC Concentrate (Example 7); (4) 4.5 kg (10.00 lbs). Ultra-dry Low aromatic heptanes (Example 4); (5) 1.4 kg (3.00 lbs.) Propane; (5a) Nitrogen gas at 55 kPa (80 psig.); (5b) Mixing on Seesaw Shaker for 10 min.
- a 17 litre (4.5-gallon) cylinder of Soft Spray is prepared as is described in Example 12 except flammable solvents Pentane and HFC-152a are substituted for HCFC-141B and HFC-134a respectively.
- the weighing and preparation sequence is: (1) 0.45 kg (1.00 lb.) Ultra-Dry Isopropanol (Example 3); (2) 3.9 kg (8.50 lbs.) Ultra-dry Isopentanes (Example 4); (3) 1 kg (2.125 lbs.) PMPC Concentrate (Example 7); (4) 3.9 kg (8.50 lbs.) Ultra-dry Isopentanes (Example 4); (5) 1.4 kg (3.00 lbs.) HFC-152a; (5a) Nitrogen gas at 55 kPa (80 psig.); (5b) Mixing on Seesaw Shaker for 10 min.
- Aerosol - 3M HFE-7100 (methoxy-nonafluorobutane) & HFC-134a
- a number of aerosol spray cans are filled with a non-flammable aerosol spray as follows.
- a non-pressurized formulation of solvents and concentrate is loaded into a stainless steel tank under nitrogen gas in the following order: (1) Ultra-dry 3M HFE-7100 18kg (40.0 lbs.) (Example 4) (2) PMPC Concentrate 4kg (8.0 lbs.) (Example 7) (3) Ultra-dry 3M HFE-7100 18kg (40.0 lbs.) (Example 4)
- the tank is closed and mixed, upside down, on a seesaw shaker for one hours, left stand over night and mixed again for one hour.
- the formulation is pressurized with 68 kPa (ten psig) of nitrogen gas, and is loaded 650 grams per unit into welded steel, epoxy-phenolic lined pint aerosol cans which are crimped closed with an all-steel, except neoprene gaskets, aerosol male tilt valve.
- the cans are pressurized with 125 grams of HFC-134a pressurized to 760 kPa (110 psig) with nitrogen gas through the valve using a pressure burette, and subsequently mixed by vigorous manual shaking.
- a number of aerosol spray cans are filled with a non flammable aerosol spray as in Example 15 except the HFC-134a propellant is replaced with HFC-152a on a molecular weight basis.
- the cans are pressurized with 100 grams of HC-152a as in Example 15.
- a number of aerosol spray cans are filled with a flammable aerosol spray.
- the following non-pressurized formulation of solvents and concentrate is weighed (directly from their ultra-drying drums or filtrate container) into a 61 litre (16-gallon) stainless steel mixing tank under nitrogen gas in the following order: (1) Ultra-dry Low aromatic heptanes 9kg (20 lbs.) (Example 4) (2) Ultra-dry Isopentanes 9kg (20 lbs.) (Example 4) (3) PMPC concentrate 4 kg (9 lbs.) (Example 3) (4) Ultra-Dry Isohexanes 27kg (60 lbs.) (Example 4)
- the tank is closed and mixed upside down on a seesaw shaker for two hours, and then pressurized with 68 kPa (10-psig) nitrogen gas.
- 68 kPa (10-psig) nitrogen gas welded, tin-free steel, aerosol cans, lined with an epoxy-phenolic coating, are filled 350 gms/can, and crimped shut with an all-steel, except neoprene gaskets, tilt-type, male, aerosol valve.
- the cans are pressurized through the valve with 65 grams of propane using a pressure burette transferred with 828 kPa (120-psig) nitrogen gas pressure and mixed manually by vigorous hand shaking.
- a number of aerosol spray cans are filled with a flammable aerosol spray as described in Example 17 according to the following formula: (1) Ultra-dry Isopentanes 18kg (40 lbs.) (Example 4) (2) PMPC concentrate 4 kg (9 lbs) (Example 3) (3) Ultra-Dry Isopentanes 18 kg (40 lbs.) (Example 4)
- the tank is pressurized with 68 kPa (10-psig) nitrogen gas, and the aerosol cans are filled 300 gms/can, and crimped shut with a metal/plastic, female aerosol valve.
- the cans are pressurized through the valve with 75 grams of HFC-152a using a pressure burette pressurized with 690 kPa (100-psig) nitrogen gas.
- a number of aerosol spray cans are filled with a flammable aerosol spray as described in Example 17 according to the following formula: (1) Ultra-dry Isopentanes 18kg (40 lbs.) (Example 4) (2) PZPC concentrate 4 kg (9 lbs.) (Example 3) (3) Ultra-Dry Isopentanes 18 kg (40 lbs.) (Example 4)
- the tank is pressurized with 68 kPa (10-psig) nitrogen gas, and the aerosol cans are filled 300 gms/can, and crimped shut with a metal/plastic, female aerosol valve.
- the cans are pressurized through the valve with 75 grams of HFC-152a using a pressure burette pressurized with 690 kPa (100-psig) nitrogen gas.
- Aerosol spray cans prepared according to the above examples may malfunction and clog as a consequence of inadvertent moisture contamination following manufacture and delivery. This malfunction can be avoided by preventing the moisture in air from contacting the valves as follows using a moisture barrier film (e.g., polyvinylidene chloride film (Dow Chemical Saran Wrap 8)) and desiccant (e.g., United Technologies silica gel or UOP M/S 3A).
- a moisture barrier film e.g., polyvinylidene chloride film (Dow Chemical Saran Wrap 8)
- desiccant e.g., United Technologies silica gel or UOP M/S 3A.
- a number of glass quart bottles are filled with a flammable deacidification solution as follows.
- a non-pressurized formulation of solvent and concentrate is loaded into a stainless steel tank under nitrogen gas in the following order: (1) Ultra-dry Low aromatic heptanes 18kg (40.0 lbs.) (Example 4) (2) PMPC concentrate 4kg (9.0 lbs.) (Example 3) (3) Ultra-dry Isopentanes 18 kg (40.0 lbs.) (Example 4)
- the tank is closed and mixed, upside down, on a seesaw shaker for two hours.
- the formulation is pressurized with 68 kPa (ten psig) of nitrogen gas, and transferred using Teflon tubing, 850 grams per unit, into glass quart bottles.
- the bottles are closed with a conventional plastic threaded cap whose liner (gasket) is composed of paperboard covered with a sealing composite composed of. aluminum foil covered with a Mylar (polyester terephthalate) plastic film or equivalent barrier material to prevent the inward migration of moisture from ambient air.
- the bottles are shaken subsequently vigorously manually to insure mixing.
- the resulting solution may be applied by dipping, brushing, spraying or other technique to thoroughly wet paper objects.
- This solution can also be prepared in steel cylinders for spray application with nitrogen gas pressure, steel, phenolic-epoxy lined, or stainless steel cans, and other sizes of glass bottles, etc. with appropriate barrier closures as desired. Up to 10 percent, typically 3 to 5 percent, by weight of co-solvents bromopropane and/or diethylene chloride may be added to improve solubility of PMPC concentrate if desired.
- the proportions of the aliphatic solvents may be varied to customize the rate of drying from and treatment penetration into paper, and indirectly control the evolution of solvent vapors into workroom air.
- composition of the two papers tested is as follows:
Abstract
Description
adding carbon dioxide and a metal in the form of metal chips or a metal alkoxide, the metal being selected from aluminium, magnesium or zinc, to the ultra-low moisture alcohol to form an organic metal carbonate composition and submicron-sized, magnetically susceptible impurities;
magnetically removing the submicron-sized magnetic impurities from the composition;
filtering the resulting organic metal carbonate composition through a submicrometer filter to produce a deacidification treatment concentrate;
and blending the deacidification treatment concentrate with additional solvent having a moisture content of less than 100 ppm comprising an aliphatic hydrocarbon and/or a hydrofluorocarbon to prepare the deacidifying composition.
Sample | pH Control | pH Treated1 | Alkaline Reserve treated |
Book A | 3.78 ± 0.00 | 9.04 ± 0.02 | 0.65 ± 0.03 |
Book B | 5.23 ± 0.03 | 9.05 ± 0.01 | 0.71 ± 0.02 |
Book C, Paper #5 | 6.24 ±0.05 | 8.71 ± 0.02 | 0.96 ± 0.04 |
Book C, Paper #6 | 5.23 ± 0.02 | 9.69 ± 0.00 | 0.91 ± 0.01 |
(1) Ultra-dry 3M HFE-7100 | 18kg (40.0 lbs.) | (Example 4) |
(2) PMPC Concentrate | 4kg (8.0 lbs.) | (Example 7) |
(3) Ultra-dry 3M HFE-7100 | 18kg (40.0 lbs.) | (Example 4) |
(1) Ultra-dry Low aromatic heptanes | 9kg (20 lbs.) | (Example 4) |
(2) Ultra-dry Isopentanes | 9kg (20 lbs.) | (Example 4) |
(3) PMPC concentrate | 4 kg (9 lbs.) | (Example 3) |
(4) Ultra-Dry Isohexanes | 27kg (60 lbs.) | (Example 4) |
(1) Ultra-dry Isopentanes | 18kg (40 lbs.) | (Example 4) |
(2) PMPC concentrate | 4 kg (9 lbs) | (Example 3) |
(3) | 18 kg (40 lbs.) | (Example 4) |
(1) Ultra-dry Isopentanes | 18kg (40 lbs.) | (Example 4) |
(2) PZPC concentrate | 4 kg (9 lbs.) | (Example 3) |
(3) | 18 kg (40 lbs.) | (Example 4) |
(1) Ultra-dry Low aromatic heptanes | 18kg (40.0 lbs.) | (Example 4) |
(2) PMPC concentrate | 4kg (9.0 lbs.) | (Example 3) |
(3) | 18 kg (40.0 lbs.) | (Example 4) |
- Paper A:
- an acid fine paper made of 50% hardwood bleached kraft, 50% softwood bleached kraft (post-industrial), 4% filler (clay), alum-rosin sizing and starch
- Paper B:
- an acid newsprint made of 100% thermomechanical pulp (TMP) with alum-rosin sizing
Testing Data | ||||
Sample | Aging Time (Days) | Number of double folds (at 500 g) | Cold Extraction (pH) | Alkaline reserve (%) |
A1 | 0 | 1186 ± 98 | 5.24 ± 0.04 | -- |
50 | 39 ± 6 | 4.74 ± 0.01 | --- | |
A2 | 0 | 1499 ± 171 | 9.47 ± 0.10 | 1.65 ± 0.58 |
50 | 1199 ± 110 | 10.19 ± 0.10 | 1.79 ± 0.17 | |
A3 | 0 | 1294 ± 133 | 9.68 ± 0.03 | 1.94 ± 0.04 |
50 | 849 ± 129 | 10.12 ± 0.04 | 1.74 ± 0.14 | |
A4 | 0 | 1467 ± 159 | 10.28 ± 0.02 | 5.75 ± 0.23 |
50 | 956 ± 127 | 10.57 ± 0.02 | 5.38 ± 0.18 | |
A5 | 0 | 1320 ± 164 | 9.80 ± 0.06 | 1.98 ± 0.16 |
50 | 853 ± 87 | 10.13 ± 0.06 | 1.64 ± 0.12 | |
A6 | 0 | 1467 ± 151 | 9.67 ± 0.08 | 2.12 ± 0.17 |
50 | 865 ± 122 | 10.34 ± 0.10 | 2.15 ± 0.21 | |
A7 | 0 | 1131 ± 121 | 9.74 ± 0.20 | 2.69 ± 0.22 |
50 | 813 ± 98 98 | 10.42 ± 0.07 | 2.55 ± 0.30 | |
A8 | 0 | 1121 ± 152 | 9.78 ± 0.01 | 2.33 ± 0.11 |
50 | 612 ± 72 | 10.20 ± 0.07 | 1.95 ± 0.43 | |
B1 | 0 | 1020 ± 108 | 5.51 ± 0.08 | --- |
50 | 115 ± 12 | 4.82 ± 0.08 | --- | |
B2 | 0 | 929 ± 87 | 10.03 ± 0.11 | 1.71 ± 0.46 |
50 | 690 ± 70 | 9.30 ± 0.92 | 0.44 ± 0.30 | |
B3 | 0 | 1065 ± 91 | 10.29 ± 0.04 | 2.98 ± 0.39 |
50 | 690 ± 77 | 10.41 ± 0.09 | 1.79 ± 0.49 | |
B4 | 0 | 1059 ± 125 | 10.51 ± 0.04 | 5.05 ± 0.57 |
50 | 422 ± 60 | 10.67 ± 0.07 | 5.98 ± 0.40 | |
B5 | 0 | 819 ± 141 | 10.29 ± 0.09 | 2.59 ± 0.10 |
50 | 713 ± 128 | 10.41 ± 0.08 | 2.11 ± 0.26 | |
B6 | 0 | 1037 ± 139 | 10.31 ± 0.13 | 3.53 ± 0.32 |
50 | 692 ± 109 | 10.49 ± 0.10 | 2.38 ± 0.47 | |
B7 | 0 | 1111 ± 143 | 10.38 ± 0.10 | 4.18 ± 1.70 |
50 | 627 ± 71 | 10.54 ± 0.01 | 3.10 ± 0.15 | |
B8 | 0 | 932 ± 101 | 10.32 ± 0.02 | 3.27 ± 0.17 |
50 | 501 ± 64 | 10.50 ± 0.07 | 2.52 ± 0.40 |
Claims (11)
- A composition for deacidifying a printed cellulosic material comprising in solution:0.1 - 4 wt.% of at least one of an organic magnesium carbonate, an organic aluminium carbonate and an organic zinc carbonate;0 - 10 wt.% of a C1 - C4 alcohol having a moisture content of less than 100 ppm; and86 - 99 wt.% of a solvent having a moisture content of less than 100 ppm comprising an aliphatic hydrocarbon and/or a hydrofluorocarbon.
- A composition according to Claim 1, comprising 0.5 - 10 wt. % of the C1 - C4 alcohol.
- A composition according to Claim 2, wherein the alcohol has a moisture content of less than 50 ppm.
- A composition according to Claim 3, wherein the alcohol has a moisture content of less than 25 ppm.
- A composition according to any preceding Claim, wherein the solvent has a moisture content of 5 - 15 ppm.
- A composition according to any preceding Claim, wherein the hydrofluorocarbon is HFC-134a (tetrafluoroethane).
- A composition according to any of Claims 1-5, wherein the solvent is a C1 - C8 aliphatic hydrocarbon.
- A method for preserving an acidic printed cellulosic material comprising the steps of:thoroughly drying the printed cellulosic material under vacuum;contacting the material with a deacidification composition as defined in any preceding Claim; andremoving the deacidified printed cellulosic material from the composition.
- A method for making a composition for deacidifying printed cellulosic materials comprising:treating a C1 - C4 alcohol with a molecular sieve or other desiccant to reduce the moisture content thereof below 100 ppm to produce an ultra-low moisture alcohol;adding carbon dioxide and a metal in the form of metal chips or a metal alkoxide, the metal being selected from aluminium, magnesium or zinc, to the ultra-low moisture alcohol to form an organic metal carbonate composition and submicrometer-sized, magnetically susceptible impurities;magnetically removing the submicrometer-sized magnetic impurities from the composition;filtering the resulting organic metal carbonate composition through a submicrometer filter to produce a deacidification treatment concentrate; andblending the deacidification treatment concentrate with additional solvent having a moisture content of less than 100 ppm comprising an aliphatic hydrocarbon and/or a hydrofluorocarbon to prepare the deacidifying composition.
- A method according to Claim 9, wherein the ultra-low moisture alcohol has a moisture content of less than 50 ppm.
- A method according to Claim 9 or Claim 10, wherein the hydrofluorocarbon is HFC-134a (tetrafluoroethane).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7110398P | 1998-01-09 | 1998-01-09 | |
US71103P | 1998-01-09 | ||
PCT/US1999/000434 WO1999035207A1 (en) | 1998-01-09 | 1999-01-08 | Deacidification treatment of printed cellulosic materials |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1060220A1 EP1060220A1 (en) | 2000-12-20 |
EP1060220A4 EP1060220A4 (en) | 2001-08-01 |
EP1060220B1 true EP1060220B1 (en) | 2003-07-23 |
Family
ID=22099279
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99901377A Revoked EP1060220B1 (en) | 1998-01-09 | 1999-01-08 | Deacidification treatment of printed cellulosic materials |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1060220B1 (en) |
JP (1) | JP2002500289A (en) |
AT (1) | ATE245685T1 (en) |
BR (1) | BR9906824A (en) |
CA (1) | CA2317564A1 (en) |
DE (1) | DE69909762T2 (en) |
ES (1) | ES2201660T3 (en) |
WO (1) | WO1999035207A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5290699A (en) * | 1998-07-31 | 2000-02-28 | Universitat Politecnica De Catalunya | Product for desacidification of cellulose material, production and utilization thereof |
SK287845B6 (en) | 2007-09-18 | 2012-01-04 | Stu Fakulta Chemickej A Potravinarskej Technologie | Multifunction device for modification of cellulose materials and method for modification of cellulose materials |
US20120286502A1 (en) * | 2011-05-13 | 2012-11-15 | Xerox Corporation | Storage Stable Images |
CN112391872B (en) * | 2019-08-16 | 2022-10-11 | 鼎纳科技有限公司 | Using method of large book deacidification system |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969549A (en) * | 1974-12-24 | 1976-07-13 | The United States Of America As Represented By The Librarian Of Congress | Method of deacidifying paper |
US4182801A (en) * | 1976-09-30 | 1980-01-08 | The Badger Company, Inc. | Method of drying liquid olefin monomer feed in a molecular sieve dryer in the polymerization of olefins from liquid olefin monomer |
US4318963A (en) * | 1980-01-21 | 1982-03-09 | Smith Richard D | Treatment of cellulosic materials |
US4401810A (en) * | 1981-09-08 | 1983-08-30 | United States Of America As Represented By The Librarian Of Congress | Method of stabilizing felted cellulosic sheet material with an alkali metal borohydride |
US5094888A (en) * | 1990-02-20 | 1992-03-10 | Fmc Corporation | Strengthening cellulosic materials |
US5264243A (en) * | 1992-06-16 | 1993-11-23 | Fmc Corporation | Mass cellulose deacidification process |
-
1999
- 1999-01-08 WO PCT/US1999/000434 patent/WO1999035207A1/en not_active Application Discontinuation
- 1999-01-08 CA CA002317564A patent/CA2317564A1/en not_active Abandoned
- 1999-01-08 JP JP2000527597A patent/JP2002500289A/en active Pending
- 1999-01-08 ES ES99901377T patent/ES2201660T3/en not_active Expired - Lifetime
- 1999-01-08 BR BR9906824-9A patent/BR9906824A/en not_active Application Discontinuation
- 1999-01-08 AT AT99901377T patent/ATE245685T1/en not_active IP Right Cessation
- 1999-01-08 EP EP99901377A patent/EP1060220B1/en not_active Revoked
- 1999-01-08 DE DE69909762T patent/DE69909762T2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP1060220A4 (en) | 2001-08-01 |
CA2317564A1 (en) | 1999-07-15 |
DE69909762D1 (en) | 2003-08-28 |
ATE245685T1 (en) | 2003-08-15 |
DE69909762T2 (en) | 2004-04-15 |
JP2002500289A (en) | 2002-01-08 |
EP1060220A1 (en) | 2000-12-20 |
BR9906824A (en) | 2000-10-17 |
WO1999035207A1 (en) | 1999-07-15 |
ES2201660T3 (en) | 2004-03-16 |
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