EP2553165B1 - Verfahren zur reduzierung des metallgehalts in gebleichter pulpe bei gleichzeitiger reduzierung der bleichungskosten in einem chemischen aufschlussverfahren - Google Patents

Verfahren zur reduzierung des metallgehalts in gebleichter pulpe bei gleichzeitiger reduzierung der bleichungskosten in einem chemischen aufschlussverfahren Download PDF

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Publication number
EP2553165B1
EP2553165B1 EP11766310.4A EP11766310A EP2553165B1 EP 2553165 B1 EP2553165 B1 EP 2553165B1 EP 11766310 A EP11766310 A EP 11766310A EP 2553165 B1 EP2553165 B1 EP 2553165B1
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Prior art keywords
urea hydrochloride
pulping
oxidizer
pulp
bleaching
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EP11766310.4A
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English (en)
French (fr)
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EP2553165A2 (de
EP2553165A4 (de
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Michael Blackstone
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Chemstone Inc
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Chemstone Inc
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    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites

Definitions

  • the majority of corrugated boxes, paper grocery bags, fine papers, and market pulps are produced by a sulfate pulping process known as "Kraft" pulping.
  • Kraft pulping wood chips are added to an aqueous medium.
  • the liquor in which the wood chips are cooked comprises a mixture of black and white liquor, the black liquor being liquor added back to the cooking vessel, or digester, from a prior batch of wood chips and the white liquor being a freshly prepared alkaline solution as described below.
  • Black liquor varies considerably among different mills depending on the white liquor used, the wood employed, and the method of cooking.
  • Typical white liquor is a solution of sodium hydroxide, sodium carbonate, sodium sulfate, sodium sulfide and various inorganic materials. White liquor solubilizes the pulp and removes the lignin from the wood fibers as described below.
  • the largest part of the organic matter removed from the wood during cooking is combined chemically with sodium hydroxide in the form of sodium salts.
  • Some of these compounds are resin soaps which account for the intense foaming properties of black liquor.
  • organic sulfur compounds and mercaptans which give the characteristic odor to the sulfate-containing black liquor, and small amounts of sodium sulfate, silica and other impurities such as lime, oxide, alumina, potash, and sodium chloride can be present in the black liquor.
  • the reaction conditions present during the cook, or digestion cause lignin, the amorphous polymeric binder found in wood fibers, to be hydrolyzed.
  • wood chips are digested only long enough to dissolve sufficient lignin to free the cellulosic wood fibers but maintain sufficient lignin intact to provide added strength to the paper.
  • the pulping process attempts to maximize pulp yield, which is defined as the dry weight of pulp produced per unit dry weight of wood consumed.
  • Bleaching typically involves contacting the pulp with an oxidizer, such as a chlorine compound, for example, chlorine dioxide, or with an oxygen compound, such as ozone, oxygen, peroxide, or the like.
  • an oxidizer such as a chlorine compound, for example, chlorine dioxide
  • an oxygen compound such as ozone, oxygen, peroxide, or the like.
  • the effectiveness of bleaching is highly pH dependent, The respective pH levels can be adjusted downwards as necessary by adding thereto pH adjusters such as acids or materials that will form acids in aqueous solution, such as sulfur dioxide, sulfuric acid, hydrochloric acid, or the like.
  • pH adjusters can form insoluble sulfates, such as calcium sulfate, barium sulfate, and the like which are insoluble and unwashable.
  • the metals and other impurities tend to remain associated with the fiber and are not washed out of the stock so that as the pH changes through the remaining processing, they tend to form scales on washer facewires, piping, and other associated equipment.
  • pH adjusters can also convert transition metals such as iron and manganese to their highly colored sulfate form, resulting in brightness reversion and the need for additional bleaching to compensate for such brightness reversion. The costs associated with removing scaling and maintaining bleaching can be significant.
  • a method of decreasing the amount of oxidizer required by a pulping or papermaking process comprising adding to a process stream or solution of the pulping or papermaking process urea hydrochloride to reduce the amount of oxidizer required by the pulping or papermaking process wherein the oxidizer comprises chlorine dioxide, ozone, oxygen, hydrogen peroxide, or combinations thereof is provided.
  • a method of reducing one or more metals, impurities, or combinations thereof from a pulping or papermaking process comprises adding to a process stream or solution containing pulp, metals, impurities, or combinations thereof of the pulping or papermaking process an effective amount of urea hydrochloride to reduce metals, impurities, or combinations thereof from the pulping or papermaking process.
  • the present disclosure is directed to methods to reduce scaling and bleaching cost in a chemical pulping process. Also described is a method to remove metals and other impurities from the bleached pulp.
  • the methods include utilizing urea hydrochloride in place of and/or in addition to certain pH adjusters in a pulping process
  • urea hydrochloride in paper and pulp processing has been previously described in U.S. Patent No. 7,029,553 to Williams et al.
  • Williams et al. describes that urea hydrochloride can be used to adjust the pH of a process stream and reduce the amount of sulfuric acid used in a papermaking process.
  • Williams et al. also describes that urea hydrochloride forms calcium chloride when it comes into contact with solutions to which calcium hydroxide has been added.
  • Williams et al. fails to teach or suggest the removal of metals and/or other impurities from a pulping process.
  • Williams et al. fails to recognize that a reduction in oxidizer can be realized by the use of urea hydrochloride.
  • the present disclosure overcomes the shortcomings of the prior art in that the methods disclosed herein result in lower processing costs by reducing scaling and bleaching costs.
  • the use of urea hydrochloride to remove metals and other impurities from pulp Also described herein is the use of urea hydrochloride to reduce brightness reversion in bleached pulps caused by oxidation of certain metals to their highly colored states.
  • urea hydrochloride can minimize the amount of oxidizer used for bleaching.
  • the methods of the present disclosure utilize urea hydrochloride in place of and/or in addition to certain pH adjusters in a pulping process, particularly a bleaching process.
  • pH adjusters typically include acids or materials that will form acids in aqueous solution, such as sulfur dioxide, sulfuric acid, hydrochloric acid, or the like.
  • urea hydrochloride can be used in addition to or as a substitution for any suitable pH adjuster as would be known in the art.
  • the urea hydrochloride used in accordance with the present disclosure can be formed from any desired ratio of urea and hydrochloric acid that performs the desired function of metal removal.
  • Urea hydrochloride suitable for use in the present invention can be prepared by mixing urea with hydrochloric acid at the desired ratio.
  • a suitable method for preparing a 1:1 molar ratio urea hydrochloride salt is described in Example 1 of U.S. Pat. No. 5,672,279 .
  • Suitable urea hydrochloride compositions are also commercially available.
  • NOVOC A-Cl (Peach State Labs, Inc., Rome, Ga.), which is a 1:1 molar ratio aqueous urea sulfate solution containing 0.25% of a quaternary amine corrosion inhibitor.
  • the methods of the present disclosure are described as being used in a Kraft pulping process.
  • the present disclosure is not to be so limited. Any of the various equivalent wood cooking processes having the production of paper as its ultimate goal may also be employed. However, the Kraft process is described in more detail as follows.
  • suitable trees are harvested, debarked and then chipped into suitable size flakes or chips.
  • the wood chips that can be processed into pulp using the chemical pulping process of the present disclosure can be either hardwoods, softwoods or mixtures thereof. Such wood chips are sorted with the small and the large chips being removed. The remaining suitable wood chips are then moved to a digester.
  • the digester is a vessel for holding the chips and a digesting composition.
  • the digester is sealed and the digester composition is heated to a suitable cook temperature under high pressure. After an allotted cooking time at a particular temperature and pressure in the digester, the digester contents (pulp and black liquor) are transferred to a holding tank. The pulp in the holding tank is transferred to the brown stock washers while the liquid (black liquor formed in the digester) is sent to the black liquor recovery area. The black liquor is evaporated to a high solids content in evaporators.
  • the Kraft cook is highly alkaline, usually having a pH of 10 to 14, more particularly 12 to 14.
  • a Kappa number corresponds directly to the amount of lignin remaining in the pulp. Generally, the higher the Kappa number, the more lignin present in the pulp and, therefore, the higher the pulp yield.
  • the Kappa number generally decreases as the digestion time is increased or the alkalinity of the cooking liquor is increased. The goal in such Kraft papermaking processes is to retain as much lignin as possible in order to enhance strength and to reduce the cost, while maintaining the uniformity of the cook. More uniform cooks result in a decreased percentage of rejects and, thereby, reduce costs for running paper mills.
  • Cooking, or digestion, of the pulp may be terminated when the amount of rejects in the pulp is reduced to an acceptable level. Substantial yield and quality advantages are achieved if the wood chips are cooked to a higher lignin content. As a result, an increase in a Kappa number target by the use of thinner chips can result in a substantial cost savings.
  • the thickness of chips obtainable on a commercial scale is always variable, A major portion of the total rejects frequently originate from a relatively small fraction of the chips having the greatest thickness. The objective in every pulping process is to achieve a lower percentage of rejects.
  • Bleaching results in a whiter, brighter paper.
  • Bleaching typically involves contacting the pulp with an oxidizer, such as a chlorine compound, for example, chlorine dioxide, or with an oxygen compound, such as ozone, oxygen, hydrogen peroxide, or the like.
  • an oxidizer such as a chlorine compound, for example, chlorine dioxide
  • an oxygen compound such as ozone, oxygen, hydrogen peroxide, or the like.
  • the effectiveness of bleaching is highly pH dependent. The respective pH levels can be adjusted downwards as necessary by adding thereto pH adjusters as described herein.
  • the present inventor has determined that pH adjusters, such as sulfuric acid, convert calcium, barium, and other metals present in the pulp to a sulfate form which is insoluble and unwashable.
  • the pH adjusters also convert iron and manganese to their highly colored sulfate form. These materials tend to remain associated with the fiber and are not washed out of the stock, so as pH changes through the remaining process steps, calcium carbonate, calcium sulfate, barium sulfate, and iron and manganese oxides all form scales on washer facewires and in piping or associated equipment. Iron, manganese, copper, and the like, all catalyze the decomposition of the oxidizers and cellulose in the presence of oxygen.
  • urea hydrochloride is utilized in place of and/or in addition to the pH adjuster and can remove a significant amount of these metals as well as other impurities, such as silica. Such removal reduces the material available for scaling, or that interfere with bleaching.
  • the method of the present description is measurable, consistent, and results in pulp with significantly less metal and/or impurity contaminant. For instance, between about 5% and 75% of one or more of metals or other impurities are removed. In some described cases, between about 25% and 70% of one or more of metals or other impurities are removed while in some described cases, between about 50% and 60% of one or more of metals or other impurities are removed.
  • the resulting pulp has a metals content of from about 30 mg/kg to about 200 mg/kg.
  • Metals can include aluminum, calcium, barium, magnesium, potassium, sodium, and zinc as well as transition metals (especially manganese, copper, and iron transition metals) or combinations thereof.
  • Impurities can include one or more of sodium sulfate, silica, lime, oxide, alumina, potash, sodium chloride or combinations thereof.
  • An effective amount of urea hydrochloride is employed in a bleaching step of a chemical pulping process to improve the efficiencies of the chemical pulping processes.
  • the effective amount depends on the particular urea hydrochloride employed and other factors including, but not limited to, wood type, the digester composition, the operating conditions of the digester, the mode of addition of the compounds including any additional compounds added, as well as other factors and conditions known to those of ordinary skill in the art.
  • UCl urea hydrochloride
  • UCl urea hydrochloride
  • about 680.4 grams (1.5 lbs.) per ton of UCl was utilized in only one of the ClO 2 stages.
  • pH control can be managed by use of sulfuric acid, as is the current practice. Addition of the UCl displaces sulfuric acid within the existing control schemes.
  • the amount of oxidizer utilized in the process can be reduced when compared to a traditional chemical pulping process that does not utilize such urea hydrochloride.
  • the amount of oxidizer can be reduced by about 10% when compared to traditional processes. In certain embodiments, the amount of oxidizer can be reduced by about 15% and in still other embodiments, the amount of oxidizer can be reduced by about 20%.
  • brightness can improve from about 88% to about 90% when compared to traditional processes.
  • Hydrochloric acid is known to react with chlorate (ClO 3 ) to form chlorine dioxide (ClO 2 ) in acidic environments.
  • Chlorate is normally present in the bleach stage filtrate, so this is presumed to be responsible for some of the immediate reduction in bleaching chemical requirements.
  • the amount of oxidizer added is from about 15.9 kg to 27.2 kg (35 to 60 lbs.) per ton ClO 2 , and about 6.8 kg to 9.1 kg (15 to 20 lbs.) per ton H 2 O 2 .
  • oxidizer can include chlorine compound, for example, chlorine dioxide, or with an oxygen compound, such as ozone, oxygen, hydrogen peroxide, or the like. The effectiveness of bleaching is highly pH dependent.
  • additives can be added to the alkaline aqueous mixture in the extraction stages.
  • Typical additives include, but are not limited to, conventional additives known for use in a chemical pulping process.
  • UCl was introduced into the first chlorine dioxide bleaching stage, along with the sulfuric acid normally used for bleaching pH chemical control, and chlorine dioxide. This was a mill system utilizing a bleaching sequence of 3 chlorine dioxide stages, with two Extraction/Peroxide stages in between. The test was only 24 hours duration, so the system had not stabilized in the later stages. Also there was an upset in the brown stock washer system that resulted in a 15% higher conductivity.
  • Paper mills use the conductivity measurement to indicate the additional load of dissolved but unwashed lignin coming into the system. This would normally result in increased ClO 2 demand in the first stage, but in accordance with the methods of the present disclosure, first stage demand actually dropped by 5% (8.1 kgs/ton to 7.7 kg) (17.8 lbs/ton to 16.9).
  • Table III lists results from two trials of a mill demonstration. All “best practices” were used to remove metals, and then a portion of the sulfuric acid was replaced with urea hydrochloride. Best practices included increasing washing, increasing the quantity of sewered water, and reducing pH on the pulp dryer. Final pH was controlled to 2.8 in all cases by adjusting sulfuric acid feed. Calcium content is reduced by about 50-60%, as are the transition metals, sodium, and silica.
  • Transition metals are known to speed the decomposition of bleaching chemicals like chlorine dioxide and hydrogen peroxide. Mills often use mixtures of chelants (EDTA, DTPA, and the like) to control these materials. Others use mixtures including magnesium to form a floc with iron and manganese.
  • EDTA chelants
  • DTPA DTPA
  • Others use mixtures including magnesium to form a floc with iron and manganese.
  • pH was controlled at 2.8 with the sulfuric acid. Chlorine dioxide usage was reduced by 17% and pulp was brighter at comparable incoming kappa numbers, indicating that significant savings could be realized. Sulfuric acid was reduced as was hydrogen peroxide.
  • any ranges of values set forth in this specification are to be construed as written description support for claims reciting any sub-ranges having endpoints which are whole number values within the specified range in question.
  • a disclosure in this specification of a range of 1-5 shall be considered to support claims to any of the following sub-ranges: 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and 4-5.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Claims (9)

  1. Verfahren zum Verringern der Menge an Oxidationsmittel, die bei einem Aufschluss- oder Papierherstellungsprozess erforderlich ist, das ein Hinzufügen von Harnstoffhydrochlorid zu einem Prozessstrom oder einer Lösung des Aufschluss- oder Papierherstellungsprozesses umfasst, um die Menge an Oxidationsmittel, die bei dem Aufschluss- oder Papierherstellungsprozess erforderlich ist, zu verringern, wobei das Oxidationsmittel Chlordioxid, Ozon, Sauerstoff, Wasserstoffperoxid oder Kombinationen daraus umfasst.
  2. Verfahren nach Anspruch 1, wobei das Oxidationsmittel Chlordioxid umfasst.
  3. Verfahren nach Anspruch 1, wobei das Oxidationsmittel Wasserstoffperoxid umfasst.
  4. Verfahren nach Anspruch 1, wobei die Menge an Harnstoffhydrochlorid 6,8-27,2 kg (15-60 lbs) pro Tonne Oxidationsmittel beträgt.
  5. Verfahren nach Anspruch 2, wobei die Menge an Harnstoffhydrochlorid 15,8-27,2 kg (35-60 lbs) pro Tonne Chlordioxid beträgt.
  6. Verfahren nach Anspruch 3, wobei die Menge an Harnstoffhydrochlorid 6,8-9,07 kg (15-20 lbs) pro Tonne Wasserstoffperoxid beträgt.
  7. Verfahren nach Anspruch 1, wobei das Oxidationsmittel, das bei dem Aufschluss- oder Papierherstellungsprozess erforderlich ist, im Vergleich zu einem traditionellen chemischen Aufschlussprozess, der kein Harnstoffhydrochlorid verwendet, um mindestens 10 % reduziert ist.
  8. Verfahren nach Anspruch 1, wobei das Oxidationsmittel, das bei dem Aufschluss- oder Papierherstellungsprozess erforderlich ist, im Vergleich zu einem traditionellen chemischen Aufschlussprozess, der kein Harnstoffhydrochlorid verwendet, um mindestens 15 % reduziert ist.
  9. Verfahren nach Anspruch 1, wobei das Oxidationsmittel, das bei dem Aufschluss- oder Papierherstellungsprozess erforderlich ist, im Vergleich zu einem traditionellen chemischen Aufschlussprozess, der kein Harnstoffhydrochlorid verwendet, um mindestens 20 % reduziert ist.
EP11766310.4A 2010-03-31 2011-02-23 Verfahren zur reduzierung des metallgehalts in gebleichter pulpe bei gleichzeitiger reduzierung der bleichungskosten in einem chemischen aufschlussverfahren Active EP2553165B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/751,143 US20110240239A1 (en) 2010-03-31 2010-03-31 Methods to Reduce Metals Content of Bleached Pulp While Reducing Bleaching Cost in a Chemical Pulping Process
PCT/US2011/025845 WO2011126613A2 (en) 2010-03-31 2011-02-23 Methods to reduce metals content of bleached pulp while reducing bleaching cost in a chemical pulping process

Publications (3)

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EP2553165A2 EP2553165A2 (de) 2013-02-06
EP2553165A4 EP2553165A4 (de) 2016-08-24
EP2553165B1 true EP2553165B1 (de) 2019-03-20

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US (1) US20110240239A1 (de)
EP (1) EP2553165B1 (de)
BR (1) BR112012025085B1 (de)
CA (1) CA2795150A1 (de)
ES (1) ES2726053T3 (de)
PT (1) PT2553165T (de)
WO (1) WO2011126613A2 (de)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234466A (en) * 1992-07-24 1993-08-10 Peach State Labs, Inc. Lowering of the pH of textile processing solutions by adding urea sulfate as a pH adjusting agent
US7029553B1 (en) 1992-07-24 2006-04-18 Peach State Labs, Inc. Urea sulfate and urea hydrochloride in paper and pulp processing
US5672279A (en) 1992-07-24 1997-09-30 Peach State Labs, Inc. Method for using urea hydrochloride
CA2398329A1 (en) * 2001-08-20 2003-02-20 Hercules Incorporated Process for purifying sand
WO2005045127A1 (en) * 2003-11-07 2005-05-19 Commonwealth Scientific And Industrial Research Organisation A method for bleaching lignocellulosic materials

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* Cited by examiner, † Cited by third party
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Publication number Publication date
CA2795150A1 (en) 2011-10-13
EP2553165A2 (de) 2013-02-06
ES2726053T3 (es) 2019-10-01
EP2553165A4 (de) 2016-08-24
WO2011126613A3 (en) 2012-01-12
WO2011126613A2 (en) 2011-10-13
US20110240239A1 (en) 2011-10-06
BR112012025085B1 (pt) 2020-03-17
BR112012025085A2 (pt) 2016-06-21
PT2553165T (pt) 2019-05-30

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