EP4303358A1 - Utilisation de composés de bore dans la réduction en pâte de papier, la production de papier et la récupération caustique - Google Patents

Utilisation de composés de bore dans la réduction en pâte de papier, la production de papier et la récupération caustique Download PDF

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Publication number
EP4303358A1
EP4303358A1 EP23182956.5A EP23182956A EP4303358A1 EP 4303358 A1 EP4303358 A1 EP 4303358A1 EP 23182956 A EP23182956 A EP 23182956A EP 4303358 A1 EP4303358 A1 EP 4303358A1
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EP
European Patent Office
Prior art keywords
solution
paper
pulping
pulp
borax
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.)
Pending
Application number
EP23182956.5A
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German (de)
English (en)
Inventor
Ayhan Tozluoglu
Bilge Aslan Tanriverdi
Derya Maraslioglu
Ebru Karacay
Halil Ibrahim UGRAS
Zeki Candan
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.)
ETI MADEN ISLETMELERI GENEL MUDURLUGU
Original Assignee
ETI MADEN ISLETMELERI GENEL MUDURLUGU
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Filing date
Publication date
Application filed by ETI MADEN ISLETMELERI GENEL MUDURLUGU filed Critical ETI MADEN ISLETMELERI GENEL MUDURLUGU
Publication of EP4303358A1 publication Critical patent/EP4303358A1/fr
Pending legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes

Definitions

  • the invention relates to a method of using sodium borate compounds (borax pentahydrate and borax decahydrate) for pulp fiber, paper and caustic recovery.
  • Chemical methods can be used in pulp production from lignocellulosic raw materials (wood, annual plants, agricultural wastes, etc.).
  • Pulp is the basic raw material used in the production of writing and printing papers, all kinds of paper, cardboard and cardboard used in packaging and tissue paper, napkins, toilet paper and paper towels called cleaning papers.
  • pulp can also be used in the production of special papers for some industrial uses (e.g. insulator paper in electricity and electronics) and as the main raw material source for industries such as textiles, plastics, food, cosmetics and pharmaceuticals by enriching the cellulose content and chemically modifying it.
  • the aim of pulp production by chemical methods is to dissolve and remove the lignin, which is around 20-40% in the wood.
  • the process of removing lignin is called delignification.
  • delignification With this process, both the fibers disperse without the need for any mechanical process and the cells soften and become suitable for paper making.
  • alkali intolerant hemicellulose fractions with low molecular weight pass into the pulping solution at the very beginning of pulping.
  • the peeling, hydrolysis and oxidation reactions that occur during the kraft pulping process cause the degradation of carbohydrates, which both reduces the pulp yield and negatively affects the resistance properties of the papers obtained from the pulp.
  • the paper and pulp industry uses mechanical, chemical or a combination of these methods. Approximately 25% of pulp production is obtained by mechanical methods. Although pulp yields are high in mechanical pulp production, the disadvantage is the high consumption of electrical energy. Another disadvantage of the mechanical method is that mechanical doughs have lower resistance properties compared to chemical doughs. In chemical methods, the approach is to dissolve the lignin (delignification) under high temperature and pressure using appropriate chemicals and to separate the wood fibers from each other.
  • kraft pulp produced with the same residual lignin content using the same raw material is always obtained at a lower yield than sulfite pulp.
  • the increase in kraft pulp yield can be realized in three ways. Reducing carbohydrate loss, reducing the amount of lignin removed or a combination of these two factors.
  • anthraquinone (AQ) increases yield by stabilizing carbohydrates in the pulping medium and accelerates delignification reactions was first discovered by Holton. However, there is no significant change in the quality of the pulps obtained by kraft-AQ pulping. Although the use of additives such as polysulfide (PS) and anthraquinone (AQ) has been among the opportunities developed for improvements in basic kraft technology, neither additive has attracted significant commercial interest.
  • PS polysulfide
  • AQ anthraquinone
  • NaBH 4 has been used in the majority of studies on the effects of boron compounds on pulp and paper properties. NaBH 4 stops the possible peeling reaction by reducing the carbonyl group at the reducing end of the cellulose chain to hydroxyl group during pulping. Thus, the decrease in yield during pulping is prevented.
  • causticization stage Another important stage for producers in pulp and paper production by chemical methods is the causticization stage, which refers to the recovery of the chemicals used.
  • the main objectives of the recovery systems in the kraft process are the recovery of the inorganic pulping chemicals used, obtaining electricity and heat energy by burning the dissolved organic substances in the black liquor, recovery of valuable by-products such as tall oil and pollution prevention.
  • the recovery unit is installed to realize four main obj ectives:
  • lime (CaO) is reacted with an aqueous solution of sodium carbonate (Na 2 CO 3 ) (green liquor) to recover sodium hydroxide (white liquor).
  • the lime causticization process is carried out in three main steps:
  • the resulting lime is used for causticization, completing the calcium cycle.
  • EP1388522A2 which is in the known state of the art, a study is mentioned for improving the properties of paper produced by adding the borosilicate composition to the mixture of waste paper or primary pulp fibers or applying it to the surface of paper produced from these fibers.
  • the borosilicate materials used are preferably an aqueous solution.
  • the object of the present invention is to provide a method wherein sodium pentahydrate and borax decahydrate compounds are used to increase the efficiency of pulp (fiber), paper production and subsequent causticizing process.
  • Another object of the invention is to provide a method for improving the quality of paper by means of borax pentahydrate and borax decahydrate compounds.
  • the invention relates to pulp fiber, paper production and causticization method and includes the steps of:
  • wood was preferred as lignocellulosic biomass.
  • optimum cellulose production was achieved by using sodium borate compounds (borax penrahydrate and borax decahydrate).
  • Half-meter logs obtained from felled trees were separated into 3 cm thick discs and the bark was peeled off.
  • the knots on the disks were removed from the disks in order not to affect the results obtained in the method due to the difference in their chemical structure.
  • 3 discs were taken from each half-meter sample and chipped by hand in 0.3 ⁇ 1.5 ⁇ 3 cm dimensions. From the samples whose moisture content was determined, 400 g (oven dry) samples for each pulping were taken into polyethylene bags and stored until the pulping was carried out.
  • the pulpings were carried out in a 15 lt capacity, electrically heated, 25 kg/cm 2 pressure resistant, laboratory type rotary pulping vessel which can make 2 cycles per minute and whose temperature can be controlled thermostatically with an automatic control table.
  • the H factor value which gives the relationship between pulping time and temperature, was also calculated to control the homogeneity between the pulpings.
  • the fibers were taken in a 150 mesh sieve and washed until the washing water became clear and each fibers was opened in a fiber opener for 5 minutes each.
  • the opened fibers were screened on a Somerville type shaking vacuum sieve according to TAPPI T 275 sp-02 standard and the screened yield and residue ratios were determined as % by gravimetric measurements in the laboratory environment according to TAPPI T 210 cm-03 standard.
  • kappa numbers of the pulps were determined according to TAPPI T 236om-99 and viscosities were determined according to SCAN-CM 15-62 standard.
  • the yield, kappa and viscosity determinations some of the black solution from the firings determined as optimum for both boron compounds was taken and tested in causticization studies.
  • the concentration of the chemical used and the related cost of production as well as the kappa, viscosity and yield of the pulps were taken into consideration, and paper production was carried out from the pulps determined as optimum and compared with the control pulp.
  • the screened fibers were beaten up to 50 °SR in Hollander according to TAPPI T 200 sp-01 standard.
  • the degree of freeness of the fibers was determined by Schopper Riegler device according to ISO 5267-1 standard. 5 pieces of test papers with a weight of 90 ⁇ 2 g/m 2 were made from the pulps beaten up to 50 °SR and from the unbeaten pulps according to ISO 5269-2 standard.
  • This method involves reacting an aqueous Na 2 CO 3 solution with lime to obtain NaOH in the presence of borate to improve the causticization reaction efficiency. It is believed that this increase in efficiency is due to the buffering effect of sodium metaborate (NaBO 2 ) in alkaline solution and that sodium metaborate suppresses the concentration of hydroxyl ions on or near the surface of Ca(OH) 2 particles, allowing the equilibrium of the causticization reaction to shift to the right, thereby increasing process efficiency.
  • NaBO 2 sodium metaborate
  • the solution is prepared at 80°C.
  • the solubility of borax decahydrate, one of the sodium borate compounds, at 80°C is approximately 40 g/100 g water.
  • the solution is not saturated; it is calculated and determined according to the required B/Na ratio. For the most effective efficiency, experiments are calculated and performed according to the B/Na ratio.
  • Na 2 B 4 O 7 .5H 2 O solution 137 g Na 2 B 4 O 7 .5H 2 O per liter
  • the solution is prepared at 80°C.
  • the solubility of borax pentahydrate, one of the sodium borate compounds, at 80°C is 33.84 g/100 g water.
  • the solution is not saturated; it is calculated and determined according to the required B/Na ratio. For the most effective efficiency, experiments are calculated and performed according to the B/Na ratio.
  • green liquor was obtained from any pulp mill.
  • step 1.1.1 According to the amount of Na 2 CO 3 calculated in the previous step, the starting chemicals in step 1.1.1 were calculated and the procedure in step 1.1.2 was repeated. According to the result of the procedure, unreacted Na 2 CO 3 and causticization yield were calculated using step 1.1.3.
  • the black liquor obtained from the optimum cellulose production using sodium borate in this project was used.
  • the black liquor is not suitable for titration and causticization due to its viscous opaque nature and organic waste content. Therefore, it was pretreated before starting the experiment.
  • To characterize the salt content it was first dried and then ashed to remove all organic matter, leaving only the salts. The salts were then dissolved in deionized water and 20 ml of water was added for every 50 ml of solution. In this way the black liquor was converted into a green solution.
  • the most important parameters for paper manufacturers in pulp production are the yield, kappa number and viscosity of the pulp.
  • the inventive method it was determined that the addition of sodium borate compounds caused a general decrease in the kappa number of the pulps and an overall increase in their viscosity.
  • the addition of sodium borate compounds caused an increase in the screened yields of the pulps and a decrease in the screen residue ratio depending on the optimal use. From this point of view, it is thought that the use of sodium borate compounds in pulp production will be an advantage for pulp producers in terms of increased pulp yield as well as reduced energy consumption as a result of reaching the desired kappa number in a shorter pulping time.
  • the inventive method it was observed that the quality of the papers produced was positively affected as well as the pulp yield, viscosity and kappa.
  • the addition of sodium borate compounds increased the tensile index values of the papers and the highest tensile index increase (18.2%) was obtained with borax pentahydrate modification compared to the papers obtained from the control pulp. Tear index values were also positively affected by sodium borate modification and the highest tear index increase (45.5%) was obtained with borax decahydrate modification after the beating process.
  • the addition of sodium borate compounds also increased the burst index values of the papers. The highest burst index (37.5%) was obtained with borax pentahydrate modification in the papers obtained after the beating process.
  • Opacity one of the most important optical properties of paper, is an important feature for printing papers and envelope papers. It is more prominent especially in low weight papers. Since the thinness of the paper increases the risk of the print appearing on the back side, the opacity should be high. It was determined that the addition of sodium borate compounds used in the inventive method did not significantly change the opacity values of the papers. On the other hand, it was determined in the study that the addition of sodium borate compounds increased the brightness values of the papers. In the papers obtained after the beating process, increases of 26.2% and 26.4% were obtained for borax pentahydrate and borax decahydrate modification, respectively, compared to the control papers. As a result, it was observed that sodium borate compounds gave better results in terms of pulp and paper properties compared to control kraft pulps.
  • the effect of the addition of sodium borate compounds on the causticization of sodium carbonate in the green liquor content in kraft pulp mills was also investigated. Firstly, the effect on the aqueous solution of sodium carbonate in the laboratory environment was examined and it was determined that the addition of borax decahydrate at a molar ratio of 0.50 B/Na and borax pentahydrate at a molar ratio of 0.40 B/Na provided optimum causticization efficiency. In line with the data obtained from this study, borax decahydrate was added to the green liquor obtained from the paper mill at a molar ratio of 0.50 B/Na and borax pentahydrate was added at a molar ratio of 0.40 B / Na. It was determined that the addition of borax decahydrate improved the causticization efficiency of green liquor by 9%, while the addition of borax pentahydrate improved the efficiency by about 8%.
  • the causticization process was also performed on the solution obtained by adding borax pentahydrate and borax decahydrate during cellulose production and it was found that the addition of borax decahydrate improved the causticization efficiency by about 7% and the addition of borax pentahydrate by 3.5% compared to the green liquor taken from the paper mill.

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EP23182956.5A 2022-07-04 2023-07-03 Utilisation de composés de bore dans la réduction en pâte de papier, la production de papier et la récupération caustique Pending EP4303358A1 (fr)

Applications Claiming Priority (1)

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TR202211012 2022-07-04

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EP4303358A1 true EP4303358A1 (fr) 2024-01-10

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999063152A1 (fr) * 1998-06-01 1999-12-09 U.S. Borax Inc. Meilleur rendement de caustification de la lessive de cuisson de la pate par addition de borate
WO1999063151A1 (fr) * 1998-06-01 1999-12-09 U.S. Borax Inc. Autocaustification partielle de lessives alcalines dans les traitements de la pate de bois
EP1388522A2 (fr) 1997-09-30 2004-02-11 Ondeo Nalco Company Borosilicates colloidaux et leur utilisation dans la fabrication du papier
WO2004025020A1 (fr) * 2002-09-12 2004-03-25 Kiram Ab Processus alcalin destine a la fabrication d'une pulpe au moyen de metaborate alcalin utilise comme alcali tampon
US20050155730A1 (en) * 2004-01-20 2005-07-21 Stigsson Lars L. Method for the production of high yield chemical pulp from softwood
US7608166B2 (en) 2003-09-17 2009-10-27 International Paper Company Papers having borate-based complexing and method of making same
CA2513488C (fr) 2002-09-17 2010-12-07 International Paper Company Papiers comprenant un compose contenant du bore et procede de fabrication correspondant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1388522A2 (fr) 1997-09-30 2004-02-11 Ondeo Nalco Company Borosilicates colloidaux et leur utilisation dans la fabrication du papier
WO1999063152A1 (fr) * 1998-06-01 1999-12-09 U.S. Borax Inc. Meilleur rendement de caustification de la lessive de cuisson de la pate par addition de borate
WO1999063151A1 (fr) * 1998-06-01 1999-12-09 U.S. Borax Inc. Autocaustification partielle de lessives alcalines dans les traitements de la pate de bois
WO2004025020A1 (fr) * 2002-09-12 2004-03-25 Kiram Ab Processus alcalin destine a la fabrication d'une pulpe au moyen de metaborate alcalin utilise comme alcali tampon
CA2513488C (fr) 2002-09-17 2010-12-07 International Paper Company Papiers comprenant un compose contenant du bore et procede de fabrication correspondant
US7608166B2 (en) 2003-09-17 2009-10-27 International Paper Company Papers having borate-based complexing and method of making same
US20050155730A1 (en) * 2004-01-20 2005-07-21 Stigsson Lars L. Method for the production of high yield chemical pulp from softwood

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