US3707438A - Method for the brightening of kraft pulp with tertiary butyl hydroperoxide - Google Patents
Method for the brightening of kraft pulp with tertiary butyl hydroperoxide Download PDFInfo
- Publication number
- US3707438A US3707438A US72491A US3707438DA US3707438A US 3707438 A US3707438 A US 3707438A US 72491 A US72491 A US 72491A US 3707438D A US3707438D A US 3707438DA US 3707438 A US3707438 A US 3707438A
- Authority
- US
- United States
- Prior art keywords
- pulp
- butyl hydroperoxide
- tertiary butyl
- brightening
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title abstract description 48
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 title abstract description 48
- 238000005282 brightening Methods 0.000 title abstract description 36
- 239000002655 kraft paper Substances 0.000 title description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 96
- 238000004061 bleaching Methods 0.000 abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 14
- 239000000460 chlorine Substances 0.000 abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 7
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 47
- 239000004155 Chlorine dioxide Substances 0.000 description 24
- 235000019398 chlorine dioxide Nutrition 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000011121 hardwood Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011122 softwood Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 4
- 231100001261 hazardous Toxicity 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 241000218922 Magnoliophyta Species 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 butyl hydroperoxide-sodium hydroxide Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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
- 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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- This invention relates to a method for replacing one or more of the conventional chlorine bleaching steps of kraft pulp by the use of tertiary butyl hydroperoxide as a brightening agent in aqueous alkaline medium such as aqueous sodium hydroxide or sodium carbonate.
- Prior art Kraft brown stock as obtained from the pulping process, requires extensive treatment with chlorine and chlorine-compounds in order to obtain a bleached and brightened pulp.
- the first stage normally consists of treating with chlorine and the second stage, which follows, is an extraction with aqueous sodium hydroxide, these stages being designated C and E, respectively.
- the pulp is treated with hypochlorite, the H stage; the final brightness is obtained by treating with chlorine dioxide, the D stage.
- CEHD gives kraft pulps having a GE. brightness of 86 to 87.
- numerous five stage processes have also been designed and used, for example, CEHHD, CEHDH, CEHED, CHDED and CEDED, wherein the letters refer to the same stages as described in the four stage sequence.
- hypochlorite stage causes some damage to the cellulose with consequent loss in strength and color stability, thus sequences were developed which obviate the use of hypochlorite entirely by the substitution of chlorine dioxide, i.e. additional D stages, but these also were more expensive.
- Chlorine and chlorine dioxide are highly toxic and hazardous compounds, chlorine dioxide being highly explosive. All contact with the skin or with their vapors by employees using them must be avoided and this requires expensive and special precautions; and in addition, since they are so highly corrosive, special and expensive stainless steels must be employed in the equipment. Chlorine dioxide, in particular, is difiicult to handle since gas phases containing more than 10 percent ClO must be avoided and since water solubility is only 0.3 percent constant control and metering must be employed.
- the method of the present invention obviates all of these difiiculties.
- the present method completely avoids the pollution problems associated with the prior art method which fact is of exceedingly great importance since the public and many governmental agencies are now greatly concerned With these types of pollution and are requiring either stringent curbing or their entire elimination.
- the cost of the reagents for the instant process is either no greater or less than the chemical cost of the prior art chlorine bleaching compounds, and thus it is not as necessary to employ exactly optimum amounts of such reagents.
- critical amounts are not required to avoid color reversion as with the prior art processes. If an excess is used, it can be recovered and recycled.
- the method of the instant invention provides brightness increase comparable to that of the prior art methods without delignification so that there is no pulp yield loss.
- the present invention is completely flexible, that is it can be substituted for any one or all of the prior art stages, and thus is particularly suitable for replacing chlorine dioxide and obviating of the necessity of using two or more chlorine dioxide stages to replace hypochlorite and obtain final maximum brightness.
- the tertiary butyl hydroperoxide requires only ordinary precautions in handling, is highly stable having none of the hazardous and toxic characteristics of chlorine or chlorine dioxide. Likewise, it is not as corrosive and ordinary stainless steels can be used in fabricating the equipment.
- kraft pulps either as obtained in the form of the brown stock from the pulping stage of manufacture, or as obtained from any of the stages of conventional bleaching are treated with a mixture of tertiary butyl hydroperoxide and an alkaline compound such as sodium hydroxide or sodium carbonate in aqueous solution to provide a brightened pulp having a GE. brightness equal to or greater than that obtained by the conventional prior art methods which have been described.
- the invention is applicable to both hard wood and soft wood types of pulps, and in a particular important embodiment of the invention, the alkaline tertiary butyl hydroperoxide treatment is used to replace conventional chlorine dioxide treatment.
- the method of this invention is applicable either to kraft pulp made from hard woods (angiosperms) or soft woods (gymnosperms).
- the method of this invention can be employed with kraft pulp as it is obtained directly from the pulping processes in the form of brown stock or after any one of the conventional bleaching stages, such as the chlorination stage (C), after the chlorination and extraction stages (CE), or after the hypochlorite stage (CEH).
- the brightening method of this invention replaces the chlorine dioxide or D stage of the kraft process. This constitutes a particularly preferred embodiment of the invention.
- the method of this invention is also particularly applicable in replacing the two chlorine dioxide stages and extraction stage.
- the method can be carried out on pulps having the consistency, normally associated with kraft pulps, i.e. those ranging from 12 to percent, or lower or higher. Consistency refers to the weight percent of dry pulp in the bleaching or brightening liquor. Ordinarily, the consistency is based on air dired pulp weight, however, in the data in this application consistency is based on oven dried pulp weight.
- the brightening method of this invention can be carried out at temperatures in the range of from ambient temperatures, 20 to C., or below, to temperatures of 100 C. Temperatures in the range of from 70 C. to 85 C. are preferred in order to provide a shorter reaction time without reaching the temperature at which the hydroperoxide starts to decompose and vaporize, thereby reducing its effectiveness. Since the brightening reaction is dependent upon the temperature it may take up to two weeks at room temperature to obtain the same degree of brightening that can be obtained from as little as 15 minutes at 85 to 100 C. In general, at the preferred temperature range of from 70 C. to 85 C. times in the range of from 3 hours at the lower limit to /2 hour at the upper are preferred.
- the brightening step is ordinarily carried out at atmospheric pressures although pressures above atmospheric, for example, up to 50 p.s.i.g. may be used if desired or subsatmospheric pressures may be used, for example, a few pounds below atmospheric pressure.
- the weight percent based on the dry pulp of tertairy butyl hydroperoxide in the brightening liquor can range from about 0.5 to 50, however, from 20 to 40 weight percent based on the dry pulp is a more preferred range for both hard and soft wood pulps and when applied to brown stock or after the chlorination or chlorination and extraction stages.
- weight percent based on the dry pulp of tertiary butyl hydroperoxide in the brightening liquor is suflicient and some improvement is obtained even with from 0.5 to 2.5
- the brightening liquor can have a concentration of from about 5 to 20 weight percent tertiary butyl hydroperoxide although this is a matter of convenience and higher or lower concentrations can be employed.
- alkaline compound employed depends upon the quantity of tertiary butyl hydroperoxide employed and also upon the pH desired. In general, sufficient alkaline compound, i.e. sodium hydroxide or sodium carbonate should be used such that the pH ranges from 8 to 10.5 with a preferred range being from about 9 to 10.5.
- the method of this invention can also be carried out in more than one stage, for example, the pulp can be treated in a first stage and the brightening solution is drained from the pulp. The pulp is then treated with the solution to which tertiary butyl hydroperoxide and the alkaline compound have been added to bring the solution to the desired concentration.
- the addition of the water and brightening mixture also is useful in maintaining the desired consistency of the pulp.
- the handsheets were made in conventional manner by transferring the pulp to a Buchner funnel provided with a filter paper. The brightening solution was removed by suction and the pulp washed with several volumes of Water to assure complete removal of the solution. The Wet handsheet was oven dried at 100 C. under vacuum.
- EXAMPLE III A run was carried out in which the same pulps employed in Example I were treated in two successive stages for 6 hours at 50 C. in each stage charging 8.1 percent tertiary butyl hydroperoxide and 3.6 percent sodium hydroxide to each stage. The first treating solution was merely drained from the pulp between the stages. Thus.
- EXAMPLE V A series of runs were carried out wherein the brightening solution recovered from a previous run was fortified with additional tertiary butyl hydroperoxide and sodium hydroxide for treatment of an additional quantity of pulp in order to show that a recycle operation could be suitably employed by the method of the instant invention.
- a method for the brightening of kraft pulp which comprises contacting the pulp with an aqueous solution consisting essentially of tertiary butyl hydroperoxide and sodium hydroxide or sodium carbonate to provide a pH of between 8 and 10.5, said contacting being at a temperature in the range of from 20 C. to 100 C.
- aqueous solution contains from 0.5 to 50 weight percent of tertiary butyl hydroperoxide based on the weight of the dry pulp.
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7249170A | 1970-09-15 | 1970-09-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3707438A true US3707438A (en) | 1972-12-26 |
Family
ID=22107940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US72491A Expired - Lifetime US3707438A (en) | 1970-09-15 | 1970-09-15 | Method for the brightening of kraft pulp with tertiary butyl hydroperoxide |
Country Status (10)
Country | Link |
---|---|
US (1) | US3707438A (en) |
BE (1) | BE772260A (en) |
BR (1) | BR7105955D0 (en) |
CA (1) | CA951856A (en) |
DE (1) | DE2145212A1 (en) |
ES (1) | ES394982A1 (en) |
FR (1) | FR2107366A5 (en) |
GB (1) | GB1318131A (en) |
IT (1) | IT939406B (en) |
NL (1) | NL7112585A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3867246A (en) * | 1972-04-21 | 1975-02-18 | Degussa | Chlorine-free multiple step bleaching of cellulose |
US4797010A (en) * | 1987-09-22 | 1989-01-10 | Nabisco Brands, Inc. | Reheatable, resealable package for fried food |
-
1970
- 1970-09-15 US US72491A patent/US3707438A/en not_active Expired - Lifetime
-
1971
- 1971-08-25 CA CA121,346A patent/CA951856A/en not_active Expired
- 1971-08-26 GB GB4017271A patent/GB1318131A/en not_active Expired
- 1971-09-07 BE BE772260A patent/BE772260A/en unknown
- 1971-09-07 FR FR7132272A patent/FR2107366A5/fr not_active Expired
- 1971-09-09 DE DE19712145212 patent/DE2145212A1/en active Pending
- 1971-09-10 IT IT52813/71A patent/IT939406B/en active
- 1971-09-10 BR BR5955/71A patent/BR7105955D0/en unknown
- 1971-09-10 ES ES394982A patent/ES394982A1/en not_active Expired
- 1971-09-13 NL NL7112585A patent/NL7112585A/xx unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3867246A (en) * | 1972-04-21 | 1975-02-18 | Degussa | Chlorine-free multiple step bleaching of cellulose |
US4797010A (en) * | 1987-09-22 | 1989-01-10 | Nabisco Brands, Inc. | Reheatable, resealable package for fried food |
Also Published As
Publication number | Publication date |
---|---|
ES394982A1 (en) | 1974-03-16 |
NL7112585A (en) | 1972-03-17 |
FR2107366A5 (en) | 1972-05-05 |
BE772260A (en) | 1972-03-06 |
DE2145212A1 (en) | 1972-05-25 |
CA951856A (en) | 1974-07-30 |
GB1318131A (en) | 1973-05-23 |
IT939406B (en) | 1973-02-10 |
BR7105955D0 (en) | 1973-05-31 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ATLANTIC RICHFIELD COMPANY Free format text: MERGER AND CHANGE OF NAME;ASSIGNORS:ATLANTIC RICHFIELD COMPANY (MERGED INTO);ATLANTIC RICHFIELD DELAWARE CORPORATION (CHANGED TO);REEL/FRAME:004911/0380 Effective date: 19850314 Owner name: ARCO CHEMICAL COMPANY,PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ATLANTIC RICHFIELD COMPANY;REEL/FRAME:004911/0448 Effective date: 19870831 Owner name: ARCO CHEMICAL COMPANY, 1500 MARKET STREET, PHILADE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ATLANTIC RICHFIELD COMPANY;REEL/FRAME:004911/0448 Effective date: 19870831 |
|
AS | Assignment |
Owner name: ARCO CHEMICAL TECHNOLOGY, INC., A CORP. OF DE, DEL Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ARCO CHEMICAL COMPANY;REEL/FRAME:005010/0113 Effective date: 19880831 |