US3663357A

US3663357A - Bleaching of mechanical cellulosic pulp with ozone in the presence of a peroxygen compound

Info

Publication number: US3663357A
Application number: US20824A
Authority: US
Inventors: Norman Liebergott
Original assignee: Pulp Paper Res Inst
Current assignee: FPInnovations
Priority date: 1969-11-27
Filing date: 1970-03-18
Publication date: 1972-05-16
Anticipated expiration: 1989-05-16
Also published as: GB1274615A; DE2058232B2; FR2056606A5; FI50552C; SE354492B; AT302012B; DE2058232A1; NO127410B; DE2058232C3; CA902861A; FI50552B

Abstract

Bleaching of mechanical pulp in the form of fibers and fiber aggregates by adding a peroxygen compound to moist pulp to provide a mixture of pulp and peroxygen compound and thereafter treating said mixture with an ozone containing gaseous mixture.

Description

United States Patent [151 3,663,357 Liebergott 5] May 16, 1972 [54] BLEACHING OF MECHANICAL CELLULOSIC PULP WITH OZONE IN THE PRESENCE OF A PEROXYGEN COMPOUND App]. No.: 20,824

Foreign Application Priority Data Nov. 27, 1969 Canada ..068,520

US. Cl ..162/65, 8/111, 162/78 Int. Cl ..D21c 9/16 Field of Search 162/65, 78, 26, 28, 80;8/111 [56] References Cited UNITED STATES PATENTS 3,451,888 6/1969 Ancelle et a1 ..162/65 3,492,199 1/1970 Kindron et a1. 2,838,459 6/1958 Sprout 2,859,087 11/1958 Hawkinson ..162/78 Primary ExaminerS. Leon Bashore Assistant Examiner-Arthur L. Cobbin At!0rneyl. William Millen and Millen, Raptes and White ABSTRACT Bleaching of mechanical pulp in the form of fibers and fiber aggregates by adding a peroxygen compound to moist pulp to provide a mixture of pulp and peroxygen compound and thereafter treating said mixture with an ozone containing gaseous mixture 10 Claims, No Drawings BLEACHING OF MECHANICAL CELLULOSIC PULP WITH OZONE IN THE PRESENCE OF A PEROXYGEN COMPOUND BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the bleaching of a cellulosic pulp. More particularly, it relates to the treatment of groundwood or mechanical pulp in a moist comminuted form with gaseous ozone or ozone-bearing gases.

2. Description of the Prior Art In the conventional bleaching of mechanical pulp, the bleaching is effected to decolorize the pulp without rendering the lignin contained therein soluble. To effect such bleaching, two classes of bleaching chemicals are employed namely reducing agents and oxidizing agents.

The most commonly used reducing agents are hydrosulphides whence bleaching is conducted in the aqueous phase at 3 to 4 percent consistency, at a pH from 4.5 to 6.0, at a temperature of about 60 C. with a 1-hour retention time and normally chelating or sequestering agents are also present.

The most commonly used oxidizing agents for the bleaching of mechanical pulps are peroxides which in contrast to hydrosulphides involve an alkaline pH, a relatively high pulp consistency of 15 to 25 percent, moderate temperatures of about 60 C., and a retention time of 2 to 3 hours. Further, in such peroxide bleaching, it is necessary to have present stabilizers such as sodium silicate and magnesium sulphate in the bleach liquor to prevent decomposition thereof and further the mechanical pulp is normally pretreated at low consistency with organic chelating agents, such as sodium diethylenetriamine penta-acetate (DPTA), to remove naturally occurring trace metals in the mechanical pulps.

It has also been proposed (see Canadian Pat. No. 769,631 issued Oct. 17, 1967 to G. A. Wigren) to bleach cellulose or cellulosic compounds by adding ozone to the mixture of the hypochlorite and/or hypochlorous acid and/or chlorine solution containing free chlorine used as bleaching agent and the cellulose to be bleached. Thus, while hypochlorites have been proposed for the bleaching of mechanical pulps, it has been found that an excessive quantity of the hypochlorite is required and further that the hypochlorite attacks the lignin and carbohydrate in the mechanical pulp resulting in a substantial loss of yield of bleached pulp.

It has already been taught, in U.S. Pat. No. 2,466,633 issued Apr. 5, 1949 to G. J. Brabender et al., that shredded chemical pulp containing from 45 to 75 percent moisture may be bleached by treatment with air containing 0.5 percent ozone at a pH of 5 to 6 at room temperature.

However, it is also known (see Scoteland and Kringstad Norsk Skogindustri" Vol. 2, pages 49 and 51, 1968) that attempts to extend this treatment to the bleaching of mechanical pulp have not been entirely successful. Thus, when ozone is passed into a solution of mechanical pulp or when the ozonization is carried out with the dry matter content in the range of 30 to 40 percent, the brightness of the mechanical pulp becomes yellow and lower than the untreated pulp. To reduce this brightness loss it was proposed that the mechanical pulp be either reduced by preacetylation, or that the reaction with ozone be carried out with pulp in an acetone-water medium. Moreover, it was found that the attempts to obtain a more specific ozonization, i.e. to raise the pulp brightness and to remove the yellowing effect without preacetylation of the pulp were not successful.

SUMMARY OF THE INVENTION Advantages of the Invention An object of a broad aspect of this invention is the provision of a process for the bleaching of a mechanical pulp with ozone whereby the brightness and/or the strength properties of the pulp are enhanced.

Broad Statement of Invention By a broad concept of this invention, a process is provided for the bleaching of pulp, the process comprising carrying out the bleaching on moist pulp, having a consistency of 15 to 60 per cent by weight solids in the form of fiber and fiber aggregates by treating with a gaseous ozone-oxygen or ozone-air mixture, in the presence of a peroxygen compound containing a peroxygen equivalent of 0.025-l.0 per cent by weight, at a temperature of from 20 to C. for a period of from 1 to 60 minutes at a pH offrom 3.5 to 11.5.

According to one aspect of the present invention, the process comprises adding a small quantity of peroxygen compound containing a peroxygen equivalent of 0.025 1.0 per cent by weight of the dry pulp, then comminuting the pulp to the form of fiber and fiber aggregates having a consistency of 15 to 60 per cent by weight solids and then treating the pulp with a gaseous ozone-oxygen or ozone-air mixture at a temperature of from 20 to 80 C. for a period of from 1 to 60 minutes at a pH offrom 3.5 to 11.5.

By other aspects of the present invention, the peroxygen compound may be added during or after the pulp comminution stage. The essential feature of the invention is that the bleaching with ozone takes place in the presence of the peroxygen compound while the pulp is in the form of fiber and fiber aggregates. In other words, the peroxygen compound is added to the unbleached mechanical pulp, either prior to comminution or during comminution, e.g. by spraying the solution on the fiber and fiber aggregates. The comminuted pulp, in the form of fiber and fiber aggregates, is then passed into a reactor in which it is treated with an ozone-bearing gas for a period of from 1 60 minutes at a pH offrom 3.5 to 11.5.

The peroxygen compound may be any conventional inorganic peroxide, including hydrogen peroxide and sodium peroxide or organic peroxide including benzoyl peroxide and ditertiarybutyl peroxide.

The ozone may be prepared in concentration of 4 percent on a weight/weight basis 0 /0, using a commercial laboratory ozonizer, or may be obtained and used (with proper precautions) from pressurized tanks.

It has also been found that the improvement in the strength properties of the mechanical pulp is a function of contact time and pH when a constant fixed dosage of ozone (on 0d. pulp basis) is supplied to the pulp.

Fluffed mechanical cellulosic pulp (sometimes referred to as shredded mechanical cellulosic pulp) is the product obtained by fragmentation of a mechanical cellulosic pulp into fiber and fiber aggregates or flocks. Each discrete fiber aggregate or flock is spongy, compressible and readily gas permeable. Each of the fiber aggregates or flocks is usually of an average size of about A 1 inch in diameter and presents a fluffed-up, dry appearance even with about 40 percent by weight moisture in the cellulosic pulp. One preferred manner of flufiing or shredding the mechanical pulp to the form above-described is provided in Canadian Pat. application Ser. No. 068,411 filed Nov. 26, 1969, now Canadian Pat. No. 869,267 issued Aug. 27, 1971.

In one embodiment, the mechanical pulp may be treated with a peroxide solution of inorganic or organic nature, then comminuted or shredded as described in the above-identified Canadian patent and finally treated with an ozone-bearing gas. The resulting oxidized pulp will then have reached a suitable brightness with the strength properties suitably enhanced.

Description of Embodiments of the Invention The following are comparative examples showing the unexpected advance over the prior art obtainable by the practice of aspects of this invention.

EXAMPLE I A commercial spruce-balsam mechanical pulp, brightness 57.3 was pressed to 35 percent consistency. The pressed pulp was sprayed with a solution containing hydrogen peroxide (0.2 percent H on o.d. pulp), sodium silicate (2.5 percent Na SiO on o.d. pulp), sodium hydroxide (1 percent NaOl-l on o.d. pulp), magnesium sulphate (0.05 percent MgSO, on o.d. pulp) and water sufficient to reduce the pulp consistency to 30 percent. The pulp was then comminuted into fiber and fiber aggregates.

a. A portion of the peroxide treated pulp was placed into a vessel which was set in a bath and the temperature maintained at 40 C. for 2 hours. The final pH of the pulp was 10.9. A portion of the bleached pulp was washed and air-dried and the brightness measured. The brightness tabs were then placed in a hot air circulatory oven at 105 C. for 1 hour, then conditioned in a constant atmosphere, relative humidity 50 percent at 70 F. The brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table 1 below.

b. A portion of the peroxide treated pulp was placed in a rotary vessel which was set in a bath and the temperature maintained at 40 C. A gaseous ozone-oxygen mixture was passed into the rotary vessel so that within 5 minutes time 1.0 percent ozone on o.d. pulp basis was passed into the vessel. The pH of the moist comminuted pulp was 10.5. A portion of the bleached pulp was washed and air-dried and the brightness measured. The brightness tabs were then placed in a hot air circulatory oven at 105 C. for 1 hour, then conditioned in a constant atmosphere, relative humidity 50 percent at 70 F. The brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table 1 below.

was sprayed with a solution containing hydrogen peroxide (0.2 percent [-1 0 on o.dpulp), Sodium silicate (0.5 percent N a SiO on o.d. pulp), sodium hydroxide (0.25 percent NaOl-l on o.d. pulp), and magnesium sulphate (0.05 percent MgSO. on o.d. pulp) and water sufficient to reduce the pulp consistency to 30 percent. The pulp was then comminuted into fiber and fiber aggregates.

a. A portion of the peroxide treated pulp was placed into a vessel which was set in a bath and the temperature maintained at C. for 2 hours. The final pH of the pulp was 3.8. A portion of the bleached pulp was washed and air-dried and the brightness measured. The brightness tabs were then placed in a hot air circulatory oven at 105 C. for 1 hour, then conditioned in a constant atmosphere, relative humidity 50 percent at 70 F. The brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table 1 below.

b. A portion of the peroxide treated pulp was placed in a rotary vessel which was set in a bath and the temperature maintained at 40 C. A gaseous ozone-oxygen mixture was passed into the rotary vessel so that within 5 minutes time 1.0 percent ozone on o.d. pulp basis was passed into the vessel. The pH of the moist comminuted pulp was 3.6. A portion of the bleached pulp was washed and air-dried and the brightness measured. The brightness tabs were then placed in a hot air circulatory oven at 105 C. for 1 hour, then conditioned in a constant atmosphere, relative humidity 50 percent at 70 F. The brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table I below.

TABLE I.PROPERT1ES OF MECHANICAL PULPS 11% Ozone supplied on o.d. pulp] Elrepho Basis Breaking Brightness Example Treatment End wt., length, Burst Teal brightness after aging, number Pulp time, min. pH g./m.: km. factor factor percent percent Untreated 59. 6 3. 3 14. 6 37 57. 3 56. 1

Ozone alone 30 10. 0 58. 2

' z 1120: al0u(. 120 3. 8 50.8 3.4 14.6 36 59.2 58. 1 2(1)). 11202111115 0z0110. 5 3.6 61.3 3.6 15.5 37 63.3 62.3 2((:) d0 30 3.5 61.7 4.6 21.2 36 64.8 63.5 2((1) ()zouu alone 30 4. 1 50. J 4. 8 20. 0 37 50. 5 58.1

c. A portion of the peroxide treated pulp was placed in a roc. A portion of the peroxide treated pulp was placed in a rotary vessel which was set in a bath and the temperature maintained at 40 C. A gaseous ozone-oxygen mixture was passed into the rotary vessel so that within 30 minutes time 1 percent ozone on o.d. pulp basis was passed into the vessel. The pH of the moist comminuted pulp was 10.3. A portion of the bleached pulp was washed and air-dried and the brightness measured. The brightness tabs were then placed in a hot air circulatory oven at 105 C. for 1 hour, then conditioned in a constant atmosphere, relative humidity percent at 70 F. The brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table 1.

d. A commercial spruce-balsam mechanical pulp,

brightness 57.3, was pressed to 35 percent consistency. The pressed pulp was sprayed with a solution containing sodium hydroxide (1.5 percent NaOH on o.d. pulp and water sufficient to reduce the pulp consistency to 30 percent. The pulp was then comminuted into fiber and fiber aggregates. The shredded pulp was then placed into a rotary vessel which was set into a bath and the temperature maintained at 40 C. A gaseous ozone-oxygen mixture was passed into the vessel so that within 30 minutes 1 percent ozone on o.d. pulp basis was passed into the vessel. The pH of the moist comminuted pulp was 10.0. The pulp was then washed, air-dried and the brightness measured. The brightness is set out in Table 1.

EXAMPLE ll A commercial spruce-balsam mechanical pulp, brightness 57.3 was pressed to 35 percent consistency. The pressed pulp tary vessel which was set in a bath and the temperature maintained at 40 C. A gaseous ozone-oxygen mixture was passed into the rotary vessel so that within 30 minutes time 1 percent ozone on o.d. pulp basis was passed into the vessel. The pH of the moist comminuted pulp was 3.5. A portion of the bleached pulp was washed and air-dried and the brightness measured. The brightness tabs were then placed in a hot air circulatory oven at C. for 1 hour, then conditioned in a constant atmosphere, relative humidity 50 percent at 70 F. The brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table l.

d. A commercial spruce-balsam mechanical pulp,

brightness 57.3 was pressed to 30 percent consistency and then comminuted into fiber and fiber aggregates. The shredded pulp was then placed into a rotary vessel which was set into a bath and the temperature maintained at 40 C. A gaseous ozone-oxygen mixture was passed into the vessel so that within 30 minutes 1 percent ozone on o.d. pulp basis was passed into the vessel. The pH of the moist comminuted pulp was 4.1. The pulp was then washed, air-dried and the brightness measured. The brightness is set out in Table l.

The unexpected synergistic effect on the brightness is evident on comparing the brightness of pulp bleached with hydrogen peroxide alone, with ozone alone and with the combination of the peroxygen compound and ozone.

The preceding examples can be repeated with similar success by substituting the generically and specifically described reactants and operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Consequently, such changes and modifications are properly, equitably, and intended" to be, within the full range of equivalence of the following claims.

I claim:

1. A process for bleaching of mechanical pulp which comprises adding a peroxygen compound containing a peroxygen equivalent of 0.025 1.0 per cent by weight of the peroxygen compound on the oven dry weight of the pulp to moist pulp having a consistency of to 60 per cent by weight solids and in the form of fiber and fiber aggregates to provide a mixture of said pulp and said peroxygen compound, and thereafter treating, said resultant mixture with a gaseous mixture selected from the group consisting of ozone-oxygen, ozoneair, and mixtures thereof, until the pulp has been contacted with at least about 1 per cent by weight ozone on an oven-dry basis, said treating being conducted at a temperature of from about C. to about 80 C. for a period of from about 1 to about 60 minutes at a pH of from about 3.5 to about 11.5.

2. The process of claim 1 further including the positive step of comminuting said pulp, thereby to form said fiber and fiber aggregates.

3. The process of claim 2 wherein the comminuted pulp is in the form of fiber and fiber aggregates having an average diameter of V4 1 inch.

4. The process of claim 2 wherein the peroxygen compound is added prior to the comminution step.

5. The process of claim 2 wherein the peroxygen compound is added during the comminution step.

6. The process of claim 1 wherein the is hydrogen peroxide.

7. The process of claim 6 wherein the hydrogen peroxide is in the form of an aqueous solution.

8. The process of claim 7 wherein the aqueous solution contains hydrogen peroxide, sodium silicate, sodium hydroxide and magnesium sulphate.

9. The process of claim 1 wherein the gaseous mixture comprises ozone oxygen in concentrations of 4 percent on a weight/weight basis 0 /0 10. The process of claim 1 wherein the gaseous mixture has been prepared by passing oxygen through an ozonizer.

peroxygen compound

Claims

2. The process of claim 1 further including the positive step of comminuting said pulp, thereby to form said fiber and fiber aggregates.
3. The process of claim 2 wherein the comminuted pulp is in the form of fiber and fiber aggregates having an average diameter of 1/4 - 1 inch.
4. The process of claim 2 wherein the peroxygen compound is added prior to the comminution step.
5. The process of claim 2 wherein the peroxygen compound is added during the comminution step.
6. The process of claim 1 wherein the peroxygen compound is hydrogen peroxide.
7. The process of claim 6 wherein the hydrogen peroxide is in the form of an aqueous solution.
8. The process of claim 7 wherein the aqueous solution contains hydrogen peroxide, sodium silicate, sodium hydroxide and magnesium sulphate.
9. The process of claim 1 wherein the gaseous mixture comprises ozone - oxygen in concentrations of 4 percent on a weight/weight basis O3/O2.
10. The process of claim 1 wherein the gaseous mixture has been prepared by passing oxygen through an ozonizer.