WO2007145932A1

WO2007145932A1 - Deinking of waste paper

Info

Publication number: WO2007145932A1
Application number: PCT/US2007/013216
Authority: WO
Inventors: Cesar I. Basilio; Steven W. Sheppard
Original assignee: Thiele Kaolin Company
Priority date: 2006-06-12
Filing date: 2007-06-05
Publication date: 2007-12-21
Also published as: ES2554926T3; JP5441258B2; JP2009540146A; EP2027331A4; EP2027331A1; US20070284067A1; EP2027331B1; US8052837B2

Abstract

Waste paper can be deinked by use of a composition which comprises a surfactant and a mineral-based deinking component.

Description

DEINKING OF WASTE PAPER

TECHNICAL FIELD

The present invention relates to the deinking of waste paper. In a more specific

aspect, this invention relates to the use of a mineral-based deinking component for the

deinking of waste paper.

This invention also relates to a process for the deinking of waste paper.

BACKGROUND OF THE INVENTION

Deinked pulp has become a principal source of raw material for making paper in

applications such as newsprint and tissue production. The deinking process has evolved

throughout the years to provide for the removal of ink from recycled paper. In

conventional paper recycling processes, deinking is carried out by converting the waste

paper, such as old newspaper, old magazines and mixed office waste, to a pulp and then

contacting the pulp with an alkali for pH modification and swelling of the fiber and a

surfactant to stabilize the ink particles and reduce reattachment of the ink particles to the

fiber. The ink particles and other impurities from the pulp fiber are then released and

separated.

The current deinking processes employed in separating the ink from the fiber m

waste paper include wash deinking, flotation deinking or a combination of both methods. Flotation deinking involves the interaction between the ink particles, air bubbles and the

fibers. The ink particles which are typically rendered hydrophobic by a deinking

surfactant attach to the air bubble surfaces and float upwards towards the top of the

flotation device. Under typical conditions, the fiber will remain hydrophilic and will

neither attach to the air bubbles nor float during the flotation process. In the case of wash

deinking, the ink particles are kept well dispersed in the aqueous phase by surfactants.

The ink particles are separated from the fibers by a repeated flow of water passing by the

fibers through a screen. This wash deinking technology involves multiple dilution and

thickening stages.

In deinking, the surfactants used are either fatty acids, synthetic surfactants such as

alkoxylates or blends of these two surfactant types. Fatty acids are well known flotation

agents used in both mineral and non-mineral applications. The use of synthetic

surfactants such as alkylamine polyethers as deinking aids is described in U.S. Patents

No. 4,483,741 and 4,605,773. The use of a blend of fatty acid and alkylene oxide as a

deinking agent is described in U.S. Patent No. 4,964,949.

Another synthetic surfactant blend used in flotation deinking is a polyester

obtained through the reaction between polyalkylene glycol, carboxylic acid and/or

anhydrides and saturated fatty acids, as described in U.S. Patent No. 5,736,622.

U.S. Patents No. 5,227,019; 5,225,046; 5,725,730 and 5,801,135 disclose the use

of fatty acids with alkoxylated fatty alcohols. A flotation deinking method using alkylene

oxide, oil, fat and alcohol is described in U.S. Patent No. 6,251,220. U.S. Patents No. 5,151,155 and 5,336,372 describe a deinking process wherein

organically modified smectite clay is used.

U.S. Patent No. 5,540,814 describes a method for removing ink and reducing

stickies from waste paper by using cationic kaolin clay and a centrifugal cleaner.

Due to the limitations of these different deinking processes to separate the ink

particles from the fiber obtained from waste paper, there is a need in the industry to

develop a process that is more efficient and cost effective.

SUMMARY OF THE INVENTION The present invention provides a mineral-based deinking component for use in the

deinking of waste paper by wash deinking, flotation deinking or a combination of these

methods.

The present invention also provides a process for the deinking of waste paper in

which a mineral-based deinking component is used.

In the present invention, the increased interaction of the mineral-based deinking

component with the ink particles results in an increased efficiency of the deinking

process over other methods such as those methods utilizing deinking surfactants alone.

In the present invention, the mineral-based deinking component is prepared by

treating the mineral particles with hydrophobizing reagents and then separating the

hydrophobic mineral particles from the non-hydrophobic mineral particles. Only the

particles that are hydrophobic are used in this invention, unlike the prior art that uses the

entire treated particles without regard to their surface property. The hydrophobic nature of these surface-modified mineral particles improves their attachment to the ink particles,

resulting in improved separation of the ink particles from the fibers of the waste paper.

In addition, the ink particles in this invention are separated from the paper fibers

using flotation deinking, wash deinking or a combination thereof as comparied to the

prior art that relies on a gravity-type separator or a centrifugal device for separation.

For purposes of this applicaton, the term "deinking" will be understood to refer to

the treatment of waste paper so that the ink particles, or at least a substantial amount of

the ink particles, are separated from the waste paper which can then be recycled for future

use.

These and other objects, features and advantages of this invention will become

apparent from the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, the mixtures of mineral particles are first

dispersed into a slurry form and then mixed with a hydrophobizing agent to modify the

surface of the mineral particles.

The minerals that are used in this invention are silicate minerals such as kaolinite,

talc, quartz, mica, potash, kyanite, phosphate, zircon, smectite-type clay or feldspar;

oxide minerals such as anatase, rutile, ilmenite, cassiterite, chromite or iron oxides;

carbonates such as calcite, magnesite or dolomite, nonmetallic minerals such as barite,

sylvite or halite; or sulfide minerals such as pyrite, chalcopyrite, chalcocite or galena. A

mixture of minerals can be used in this invention. The hydrophobizing agents that may be used to prepare the surface-modified

mineral particles include but are not limited to sulfhydryls, carboxylic acids, amines, oil,

sulfonates, hydroxamates, fatty acids, siloxanes and blends thereof. The hydrophobized

mineral particles are then concentrated and separated from the non-hydrophobized

mineral particles. Methods of separating the hydrophobized minerals include flotation

and selective flocculation. In the case of flotation, the conditioned minerals are then

transferred to a flotation cell and floated. The hydrophobized mineral particles can then

be used in this invention as deinking aids for improving the deinking process compared to

that using a deinking surfactant alone.

The basic steps in a deinking process involve the following: repulping the waste

paper, coarse cleaning and screening, flotation and/or wash deinking, fine cleaning and

screening and then bleaching.

In the repulping stage, the waste paper is usually treated in aqueous alkaline

conditions with chemicals such as sodium hydroxide, sodium silicate and hydrogen

peroxide. The repulping stage may also be conducted at neutral pH conditions by

minimizing the addition of the alkali chemicals or using soda ash instead. The deinking

surfactant and the deinking component of this invention are typically added at this stage,

although these components may be added later just prior to the actual separation of the

ink stage (i.e., washing or flotation). This step is then followed by coarse cleaning or

screening to remove the relatively coarse contaminants such as staples, plastic, etc. from

the pulp. The pulp is then processed by well-known wash deinking, flotation deinking or

a combination of both. The mixtures of minerals used as the deinking component can be any of the

minerals listed previously; however, crude kaolin clay will be used to describe the

process of this invention. Crude kaolin clay generally contains kaolinite and other related

hydrated aluminum silicate minerals as well as quartz, mica, titanium dioxide and iron

oxide minerals.

To produce the surface modified kaolin clay deinking component, the starting

crude kaolin clay is initially dispersed by blunging the clay with water in the presence of

a dispersant at dosages ranging from about 1 to about 25 pounds per ton of dry solids.

Effective dispersants include sodium silicate, sodium metasilicate, sodium

hexametaphosphate, and sodium polyacrylate. The preferred dispersant for this invention

is sodium silicate using dosages ranging from about 2 to about 16 pounds per ton. The

pH is adjusted to a range of about 5 to about 11, preferably about 7 to about 10, using a

pH modifier such as sodium hydroxide, sodium carbonate or ammonium hydroxide.

The dispersed kaolin clay slurry is then mixed with hydrophobizing agents such as

an alkyl hydroxamate, fatty acid, siloxane and combinations thereof. The amount of

hydrophobizing reagent added to the dispersed kaolin slurry must be sufficient to

hydrophobize the crude kaolin clay. The hydrophobizing agent additions used are in the

range of about 0.2 to about 10 pounds per ton of dry clay, preferably about 0.5 to about 5

pounds per ton.

After mixing with the hydrophobizing reagent, the kaolin slurry is then transferred

to a froth flotation cell and, if necessary, diluted to a pulp density preferably within the

range of about 15 to about 45% solids by weight. A frother, which is generally a heteropolar surface active organic reagent, may be added if necessary to stabilize the air

bubbles. The amount of frother added depends on the type of frother used and the

amount of the kaolin feed material. The frothers that can be used include alcohols,

amines, alkoxy compounds and polyglycol compounds.

The preferred frothers for this invention are methyl isobutyl carbinol, ethyl

hexanol, pine oil and polypropylene glycol. The frother dosage for effective flotation

ranges from about 0.01 to about 2 pounds per ton, preferably about 0.05 to about 1 pound

per ton. The operation of the froth flotation machine is conducted in conventional

fashion. After an appropriate period of operation, the hydrophobized kaolin clay

materials are concentrated in the froth phase and collected.

In the production of the hydrophobized surface-modified mineral particles for the

present invention, the froth flotation process can be conducted either in a mechanical or

pneumatic machine. A typical pneumatic machine that can be used is a flotation column,

while a typical mechanical machine is an impeller driven flotation machine. The

hydrophobized material in this invention can also be produced by flotation through the

use of other flotation processes such as dissolved air flotation, induced air flotation, bulk

oil flotation, skin flotation or table flotation.

The hydroxamate agent used in the present invention is a hydroxamate compound,

or a mixture of such compounds, having the general formula:

R - C - NH

O OM in which R is an alkyl, aryl or alkylaryl group having 4 to 28 carbon atoms, and M is

hydrogen, an alkali metal or an alkaline earth metal.

Examples of suitable R groups include butyl, hexyl, octyl, dodecyl, lauryl, 2-

ethylhexyl, oleyl, eicosyl, phenyl, tolyl, naphtyl and hexylphenyl.

Examples of suitable alkali metals are lithium, sodium and potassium.

Examples of suitable alkaline earth metals are magnesium, calcium and barium.

Examples of the hydroxamates which are useful in the process of the present

invention include potassium butyl hydroxamate, potassium octyl hydroxamate, potassium

lauryl hydroxamate, potassium 2-ethylhexyl hydroxamate, potassium oleyl hydroxamate,

potassium eicosyl hydroxamate, potassium phenyl hydroxamate, potassium naphtyl

hydroxamate, potassium hexylphenyl hydroxamate, and the corresponding salts of

sodium and other alkali or alkaline earth metals. The salts can be converted to the

corresponding acids by those skilled in the art. These hydroxamate compounds can be

prepared by well-known methods.

In this invention, the fatty acid used has the general formula:

R¹ - C - OM¹

O in which R' is an alkyl, aryl or alkylaryl group having 1 to 26 carbon atoms, and M' is

hydrogen, an alkali metal or an alkaline earth metal.

Examples of suitable R' groups include methyl, ethyl, butyl, octyl, lauryl, 2-

ethylhexyl, oleyl, eicoseyl, phenyl, naphtyl and hexylphenyl. Examples of suitable alkali metals are lithium, sodium and potassium.

Examples of suitable alkaline earth metals are magnesium, calcium and barium.

The siloxanes used in the present invention are organosilane compounds

containing a silicon to carbon bond. Examples of suitable siloxanes include

hexamethyldisiloxane, hexamethylytrisiloxane, disiloxane, vmylheptamethyltrisiloxane,

octamethyltrisiloxane, tetramethyldisiloxane, and tetravinyldimethyldisiloxane.

The silicones used in the present invention have the general formula:

(R"_n - Si - O₄._n)_m

in which R" is vinyl, hydrogen or an alkyl, aryl, or alklaryl group having 1-26 carbon

atoms, n is between 0 to 3 and m is 2 or larger.

Examples of suitable R" include methyl, ethyl, butyl, octyl, lauryl, 2-ethylhexyl,

oleyl, eicoseyl, phenyl, naphtyl, hexylphenyl, vinyl and hydrogen.

Examples of silicones which are useful in the process of the invention include

polydimethylsiloxanes, polymethylhydrosiloxanes, polyethylhydrosiloxanes and

polymethylalkylsiloxanes .

The surfactants used in the composition of this invention are well-known in the

industry and include ionic, non-ionic and cationic surfactants.

The present invention is further illustrated by the following examples which are

illustrative of certain embodiments designed to teach those of ordinary skill in this art

how to practice this invention and to represent the best mode contemplated for carrying

out this invention. Example 1

A sample of kaolin clay from Washington County, Georgia was hydrophobized

and separated from the non-hydrophobized kaolin clay using the following procedure.

2000 dry grams of crude kaolin clay sample were blunged using a high speed mixer.

Blunging of the clay was conducted at 60% solids using 2.4 pounds sodium silicate per

ton of dry clay and 1.6 pounds sodium hydroxide per ton of dry clay. This dispersed

kaolin clay was then hydrophobized with the following hydrophobizing reagents: 1

pounds alkyl hydroxamate per ton of dry clay, 1 pounds tall oil per dry ton of clay and

0.5 pound calcium chloride per dry ton of clay as activator for tall oil. The

hydrophobized material was diluted to 25% solids with water and then transferred to a

Denver D-12 flotation cell. The slurry was then floated and the hydrophobized material

was then collected in the froth phase. The material was then dewatered to remove some

of the water present in the collected slurry. The hydrophobized kaolin clay material

produced in this example is used as the deinking aid in Examples 2 - 6.

Example 2

The flotation deinking test procedure used in this work is as follows. Various old

newsprint (ONP) from the Macon Telegraph, Wall Street Journal and USA Today

newspaper was shredded. 300 gm of ONP was mixed with hot tap water to 5% solids

with the following chemicals added: 2 pound calcium chloride per dry ton of ONP, 2

pound sodium silicate per dry ton of ONP, deinking surfactant and sodium hydroxide to

adjust the pH of the slurry to about pH 9 to 10. The deinking aid produced in Example 1

is added here together with the other chemicals. The sample was pulped for 10 minutes in a Formax Maelstrom Laboratory Pulper. After pulping, the sample was diluted to 1%

solids and floated in a Denver cell for five minutes. After flotation, the accepts containing

the deinked fiber was collected and its brightness measured. Brightness measurement was

conducted by forming the deinked pulp into a pad, oven dried, and the GE brightness

measured using TAPPI Test Method T-218.

The conventional technology uses a deinking surfactant only. In this example, 5

pounds of LionSurf 850 deinking surfactant per dry ton of ONP was used. (LionSurf 850

is a non-ionic polyalkylene oxide based surfactant commercially available from Vinings

Industries.) The process of this invention used 5 pounds of deinking aid produced in

Example 1 per dry ton of ONP in addition to the 5 pounds of LionSurf 850 deinking

surfactant per dry ton of ONP. The results of the deinking tests given in Table 1 show

that the addition of the hydrophobized kaolin clay deinking aid of this invention resulted

in higher brightness of the deinked pulp.

Table 1

*Blend containing equal amounts of ONP from Macon Telegraph, Wall Street Journal and USA Today.

Example 3

The flotation deinking test procedure used in Example 2 was repeated on an ONP

blend containing equal amounts of waste paper from the Macon Telegraph, Wall Street

Journal and USA Today newspaper. The conventional technology, uses a deinking surfactant only. In this example, 7.5 pounds of LionSurf 850 deinking surfactant per dry

ton of ONP was used. However, the process of this invention used 3.75 pounds of

deinking aid produced in Example 1 per dry ton of ONP in addition to the 3.75 pounds of

LionSurf 850 deinking surfactant per dry ton of ONP. The results given in Table 2 show

that replacing half of the deinking surfactant with the hydrophobized kaolin clay deinking

aid show an increase in the brightness of the deinked pulp. An improvement in deinking

was obtained even though half of the deinking surfactant was replaced by an equivalent

amount of the more cost effective deinking aid of this invention.

Table 2

Example 4

Another flotation deinking test was conducted using the flotation deinking test

procedures used in Example 2. The test used an ONP blend containing equal amounts of

waste paper from the Macon Telegraph, Wall Street Journal and USA Today newspaper.

The conventional technology used 7.5 pounds of Buckman 2349 flotation deinking

surfactant per dry ton of ONP while the process of this invention used 3.75 pounds of

deinking aid produced in Example 1 per dry ton of ONP and 3.75 pounds of Buckman 2349 flotation deinking surfactant per dry ton of ONP. (Buckman 2349 is a surfactant

commercially available from Buckman Laboratories and contains ethoxylated

propoxylated C 16- 18 alcohols.) Table 3 shows that replacing half of the deinking

surfactant with the hydrophobized kaolin clay deinking aid results in an increase in the

brightness of the deinked pulp. An improvement in deinking was obtained even though

half of the deinking surfactant was replaced by an equivalent amount of the more cost

effective deinking aid of this invention.

Table 3

Example 5

In the case of the wash deinking test, the following procedure was used in this

work. Various old newsprint (ONP) from the Macon Telegraph, Wall Street Journal and

USA Today newspaper was shredded. 300 gm of ONP was mixed with hot tap water to

5% solids with the following chemicals added:

2 pound calcium chloride per dry ton of ONP, 2 pound sodium silicate per dry ton

of ONP, deinking surfactant, and sodium hydroxide to adjust the pH of the slurry to about

pH 9 to 10. The deinking aid produced in Example 1 is added here together with the other

chemicals. The sample was pulped for 10 minutes in a Formax Maelstrom Laboratory

Pulper. After pulping, the sample was diluted to 1% solids and washed through a 325 mesh screen. The fiber remaining on the screen, which is the "accepts", is made into a

pad and the brightness of the pad is measured afterwards.

For the conventional technology, 5 pounds of LionSurf 850 deinking surfactant

per dry ton of ONP was used. The process of this invention used 5 pounds of the deinking

aid produced in Example 1 per dry ton of ONP and 5 pounds of LionSurf 850 deinking

surfactant per dry ton of ONP. The results of the washing deinking tests are shown in

Table 4. The use of the hydrophobized kaolin clay deinking aid of this invention resulted

in higher brightness of the deinked pulp.

Table 4

Example 6 The procedure used for wash deinking test used in Example 6 was repeated using

5 pounds of Buckman 2317 deinking surfactant per dry ton of ONP was used. (Buckman

2317 is a surfactant commercially available from Buckman Laboratories and is a glycol

ether-based wash deinking surfactant.) For the process of this invention, 5 pounds of

Buckman 2317 deinking surfactant per dry ton of ONP together with 2.5 pounds of

deinking aid produced in Example 1 per dry ton of ONP was used. The wash deinking test results are presented in Table 5. As shown, the hydrophobized kaolin clay deinking

aid of this invention gives improved deinking of ONP.

Table 5

This invention has been described in detail with particular reference to certain

embodiments, but variations and modifications can be made without departing from the

spirit and scope of the invention as defined in the following claims.

Claims

CLAIMSWhat is claimed is:

1. A composition for deinking waste paper, wherein the composition

comprises:

A. a surfactant and

B. a mineral-based deinking component.

2. A composition as defined by Claim 1 wherein the surfactant is ionic,

cationic, non-ionic or a blend thereof.

3. A composition as defined by Claim 1 wherein the deinking

component is hydrophobic.

4. A composition as defined by Claim 1 wherein the deinking

component comprises a mineral selected from the group consisting of silicates, oxides,

carbonates, nonmetallics, sulfides or a mixture thereof.

5. A composition as defined by Claim 1 wherein the mineral-based

deinking component is a kaolin-based deinking component.

6. A composition as defined by Claim 1 wherein the surfactant is a

non-ionic polyalkylene oxide based surfactant.

7. A process for deinking waste paper, wherein the process comprises :

A. treating the waste paper with a composition which comprises a

surfactant and a mineral-based deinking component and

B. subjecting the treated waste paper to wash deinking or flotation

deinking.

.

8. A process as defined by Claim 7 wherein the surfactant is ionic,

cationic, non-ionic or a blend thereof.

.

9. A process as defined by Claim 7 wherein the deinking component is

hydrophobic.

10. A process as defined by Claim 7 wherein the deinking component

comprises a mineral selected from the group consisting of silicates, oxides, carbonates,

nonmetallics, sulfides or a mixture thereof.

11. A process as defined by Claim 7 wherein the mineral-based deinking

component is a kaolin-based deinking component.

12. A process as defined by Claim 7 wherein the surfactant is a non-

ionic polyalkylene oxide based surfactant.

13. Deinked waste paper which has been deinked by a process which

comprises:

A. treating the waste paper with a composition which comprises a

surfactant and a mineral-based deinking component and

B. subjecting the treated waste paper to wash deinking or flotation

deinking.

14. Deinked waste paper as defined by Claim 13 wherein the surfactant

is ionic, cationic, non-ionic or a blend thereof.

15. Deinked waste paper as defined by Claim 13 wherein the deinking

component is hydrophobic.

16. Deinked waste paper as defined by Claim 13 wherein the deinking

carbonates, nonmetallics, sulfides or a mixture thereof.

17. Deinked waste paper as defined by Claims 13 wherein the mineral-

based deinking component is a kaolin-based deinking component.

18. Deinked waste paper as defined by Claim 13 wherein the surfactant

is a non-ionic polyalkylene oxide based surfactant.