DE2710309A1 - PROCESS FOR THE PRODUCTION OF ALKALICELLULOSE - Google Patents

Description

T 50 785 O

Applicant: Kemira Oy

Malrainkatu 30, SF-OO1O1 10, Finland

Process for the production of alkali cellulose

This invention relates to a process for the production of alkali cellulose from a cellulosic one Source material.

In the manufacture of fibers and films made from regenerated cellulose or in the manufacture of cellulose ethers composed of such as, for example, carboxymethyl cellulose, using cellulose-containing one Starting material, the first manufacturing phase is usually the. Preparation of alkali cellulose. Both already known processes, the manufacturing process is roughly as follows:

The pulp used as the starting material is treated with NaOH solution, the concentration of which must be high enough to convert the pulp into alkali cellulose. This treatment or mercerization is carried out either by immersing the pulp sheets in NaOH solution, or by whipping the pulp in NaOH solution into a mash or alkaline cellulose pulp containing, for example, 5% cellulose. The concentration of the NaOH solution used for mercerization is usually between 17-22 % MaOH.

The excess NaOH solution is squeezed out, so that an alkali cellulose is produced, the NaOH content of which is 15-17 % and the alpha cellulose content of 30-35% . The alkali cellulose obtained is ground or fiberized.

The alkali cellulose is pre-ripened by exposing it to the influence of oxygen in the air at a certain temperature

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of 20-60 ° C. When they are pre-mature, they tear Molecular chains, so the average molecular size is reduced. By regulating the temperature and time of ripening, the desired, average Molecular size achieved. The reaction can be triggered by catalysts such as cobalt or manganese salts be accelerated.

As an alternative, only enough NaOH solution can be added to the ground cellulose that can be used directly maintains the desired consistency of the alkali cellulose.

The cellulose-containing raw material used is usually bleached sulphite pulp or pre-hydrolyzed, bleached sulphate pulp. Particularly in the preparation of cellulose xanthate solution, or viscose from alkali cellulose, high quality demands are made on the pulp used. When preparing viscose, it is particularly important that the cellulose xanthate produced from alkali cellulose is completely soluble so that there are no difficulties in filtering the viscose. These demands will only specially manufactured for the viscose industry, so-called. Viscose pulp (dissolving pulp) meet, wherein it is sulphite or prehydrolyzed kraft pulp, which is usually 90 Alphazellulosegohalt j>.

Other pulp, especially paper sulphate pulp, so far could not be used for the production of viscose v / ground, because especially when using paper sulphate pulp a viscose that is difficult to filter is obtained, which has swollen gel and undissolved fiber parts contains. The reason for this is that the sulphate pulp is in the alkaline cooking solution on the walls The cellulose fibers do not have sufficient structural breakdowns, which are the prerequisites for the

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Formation of alkali cellulose are. In acidic cooking solution such as sulphite cooking solution or in acidic pre-hydrolysis however, such dissolution points arise through Removal of the hemi-cellulose under the action of Hydrolysis.

The pulp industry used the sulphite process (acidic cooking solution) rather than the sulphate process (alkaline cooking solution) has increasingly switched to the use of the sulphate process. New sulphite pulp mills are rarely established, and the old sulphite pulp mills are closed or switched to the sulphate process. The cause for this are both environmental protection as well as economic circumstances.

In the production of sulphite pulp, or especially in the case of pre-hydrolyzed sulphate pulp with a high alpha cellulose content, part of the alpha cellulose is lost, as a result of which the cell yield decreases. This means that the price of the finished pulp increases; it increases proportionally to the alpha cellulose content. If the alpha cellulose content is increased by 1 #, the yield decreases by approx. 3 />. Given today's price difference, viscose pulp is 30 % more expensive than ordinary pulp used by the paper industry. For this reason it would be advantageous to use, for example, paper sulphate pulp for the production of alkali cellulose, if there were no technical obstacles. Another advantage of sulphate pulp would be the low resin content and the small polydispersity, which is particularly important for the quality of the viscose fiber in terms of strength.

According to Finnish patent nos. 41543 and 41544 is it is possible using the double mercerisation procedure

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Produce filterable viscose from pulp of massive quality, like common sulphate pulp. In the process corresponding to the patent mentioned, the alkali cellulose is renewed after the pre-ripening mercerized. The disadvantage here, compared to the normal procedure, is that it is twice as necessary Mercerizing presses and the associated high investment and operating costs.

It has also been tried _for the reactivity of the AlknliZellulose to improve in that the Merzerisierlauge various adjuvants were added, but this has been successful only to a limited extent. The use of certain additives in the mercerising liquor is known and has been used to some extent by the industry. Auxiliaries were added, among other things, to disperse the resins in the cellulose, to improve fiberization or to improve xanthogenation. However, for the production of alkali cellulose, viscose cellulose (chemical fiber cellulose) was always used and the amount of additives was small.

Surprisingly, however, it has now been found that using certain substances during mercerization The reactivity of the alkali cellulose can be increased to such an extent that it can even be made from paper sulfate pulp Mercerizing a reactive alkali cellulose suitable e.g. for the production of viscose can be produced, which was not possible until now.

One of the aims of this invention was to develop a method of changing the raw material base in the viacose industry, instead of using expensive, specially refined viscose or Cheraie pulp, the use of ordinary

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Paper pulp, which is a completely different raw material than viscose pulp is to enable.

The subject of the invention is the method defined in claim 1.

The organic components added in this method according to the invention usually contain see a polyoxyethylene group or at least one hydrophobic, e.g. aliphatic chain, which is at least Contains 3 carbon atoms, as well as at least one hydrophilic group, such as the hydroxyl group, ether oxygen or ketone group. Besides these, simple hydrocarbons are effective additives.

For example, in the process outlined in this invention, the following organic additives are useful:

1. Lecithin:

Actual lecithin or phosphatidylcholine

CII ₀ -OR ₁

I ^{ά Ί}

CII ₂ -O- P ^ -0-CH ₂ -CH ₂ N ⁺ C CH ₃ ) ₃ 0 "

R «. and Rp linoleic acid and oleic acid

Phosphatidylethanolamine (15 %)

Inositol phosphatide (20 %)

Sugars, sterols, fatty acids, etc. (10 %)

Triglycerides (approx. 35 %)

x, y and ζ as well as χ + ζ each not more than 50, whereby x, y or ζ are at least 1.

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R- (C ₂ H ₄ O) _x (C ₃ H ₆ O) ₇ (C ₂ H ₄ O) ₂ H

χ, y and ζ as above

R = 1) R ₁ -O fatty alcohol e.g. myristyl, lauryl,

Stearyl, oleyl, etc.

2) 0 alkylphenol, for example R ₀ = nonyl

3) polyalcohol e.g. sorbitol

R-N

x, y and ζ as above

R = alkyl, aryl or alkylaryl, e.g. fatty amine, e.g. ethoxylation products of the myristyl, lauryl, Stearyl, oleyl, etc. amines

CU

0 = C

CII,

CH,

Methyl isobutyl ketone

6. CH _x -CII ₀ -CH -CH ₀ -CH ₀ -OH

J C. ρ C. ί

CH ₅ -CH-CH ₂ -CH ₂ -OH

OH

CIL

2 ^WW 3

CH ₃ -CH ₂ -CH-Cm-CH etc.

Butanol, prairie and secondary amyl alcohols and even higher alcohols such as hexyl and octyl alcohols

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CII

CH

CH

CII

NII 271Q3Q9

Piperidine

₀ -CH ₀ -O-CH ₀ -CH ₀ 22 2 j

8. CH ₀ -CIU-O-CH ₀ -CH I
OH

Diethylene glycol monobuty1 ether

⁹ * ^C 6 ⁿ i4 - ^{> C} 1O ^H 22

various isomers of petroleum ether boiling range + 100-12O ⁰ C

10. ⁰¹¹ O- ⁰ P ₂

OH O ethylene glycol monoethyl ether

11. CH ₀ -CH-CH-CH-CH-Ch ₀

I ² IIlI! ² OH OH OH OH OH OH sorbitol

12. CH

CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-Ch ₂ -CH ₂ triethylene glycol OH OH

13. C ₃ H ₇ -OC ₃ II ₇ di-isopropyl ether

14. (CH ₂ O),

Paraformaldehyde (polyoxymethylene)

15. CH ₃ -CH-CH ₂ and CH ₂ -CH ₂ -CH ₂ propanediols

OH OH

I OH OH

16. R NH,

e.g. stearyl or cyclohexyl amines

17. NH ₂ • C ₆ H ₁₂ . NH ₂ hexanediamine

709837/0934 Na stearate

19th NaOOC · C ^ i ₁₂ COOH _? 2710309
Na salt of pimelic acid ί
20th CH ₀ -OOC-C
ι 17 ^H 33 Glycerol ti * iol eat CII-OOC-C
I. 17 ^H 33

21. (C ₁₂ Hpt - N \ _) SO. "Lauryl pyridinium sulfate

22. R ₁ · CH · COOR ₂ Na salt of the sulfonated

• alkyl esters

SO ₅ Well

Of these additives, lecithin has proven to be the most advantageous.

Lecithin, its component! Any other phosphatides or their derivatives, are best added in the amount of 0.01-20 %, based on the amount of alpha cellulose, whereas organic ethers, esters, ketones, alcohol and / or pyridine derivatives are best added, depending on the quality of the substance, in the amount of 0.1-100 %, based on the amount of alpha cellulose.

In connection with this invention it was also surprisingly found that the increasing effect which the additives mentioned in the invention have on the reactivity of the alkali cellulose can also be used when using viscose cellulose as the starting material. In such a case, for example in the production of viscose, the amount of carbon disulfide can be reduced to approx. 20-30% of the amount of alpha cellulose, and a lower NaOH content can be used.

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AO

The invention is further illustrated by the following examples explained.

In the attached x \ u Q guide sb ei play is the Filterability or the KVM / location no standardized measurement method, the value depends on the determination method. The filterability values used here can be set as follows:

KW value piltrability

O- 50 excellent

50-100 good

100-150 mediocre

150-300 bad

300-800 particularly bad

> 800 cannot be filtered

Example 1 The bleached pine sulfate pulp commonly used by the paper industry with an alpha cellulose content of about 07 1 <> was mercerized g to a 4 # -tigen suspension (slurry) in a Merzerisierlauge whose concentration 225 was per liter, temperature 35 ⁰ C, 30 minutes .

The Merzerisierlauge further contained 10 g per liter or 25 i ^a weight of alpha cellulose, such Alkylenoxydfett-alcohol addition products whose trade name Marlox FK 64, and their manufacturers Chemische Werke Hüls AG. An alkali cellulose cake was produced from the alkali cellulose suspension by pressing, pressure ratio 3.2. The slightly alkali cellulose crumbs was 18 hours pre-matured at a temperature of +40 ⁰ C and was then sulfided for 2 hours at +30 ⁰ C, with carbon disulfide, 35 dissolved i> of the alpha cellulose amount and viscose, which

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VfJ

AA

5.3, £ HaOH and 10.2, < Cellulose and whose falling ball viscosity was 48 seconds. The filterability the viscose or the KV / value was 49

When a comparative viscosity was produced in the same way, but without Marlox FK 64, the KW value was 2778.

Example 2 The viscose was prepared as indicated irn Example 1, but instead of Marlox PK 64 contained the Merzerisierlauge 10 grams per liter or 25 is made Co. i ° of the weight of alpha cellulose such a polypropylene glycol whose average molecular weight is 400 and from Shell Chemical . The viscose contained 5.2 # NaOH and 9.6 56 cellulose, and the falling ball viscosity was 68 seconds. A KW value of 52 was achieved with this viscose.

Example 3

The viscose was produced as indicated in Example 1, but instead of Marlox FK 64 the mercerising liquor contained 10 g per liter or 25 # by weight of the alpha cellulose diethylene glycol monobutyl ether. The viscose contained 5.0 # NaOH and 9.8 $ cellulose, the falling ball viscosity was 57 seconds. A viscose KW value of 51 was achieved.

Example 4

The viscose was produced as indicated in Example 1, but instead of Marlox FK 64, the mercerising liquor contained 10 g per liter or 25 Ί »of the weight of the alpha cellulose, such a mixture of secondary amyl alcohol isomer, which contains approx. 60-56 pentanol-2 and contained approx. 36 I> 3-pentanol. The viscose contained 5.3 i> NaOH and 9.9? ° cellulose that Kug el fallvi sko si tat was 60 seconds. A viscose KW value of 53 was achieved.

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Example 5

The viscose was prepared as indicated in Example 1, but instead of Marlox FK 64 contained the Merzerisierlauge 10 g per liter or 25 ° aliphatic i of the weight of alpha cellulose, such a mixture hydrocarbons whose boiling range is 100-120 ⁰ C between +. The viscose contained 5.2 % NaOH and 9.7 % cellulose, and the falling ball viscosity was 76 seconds. A viscose KV / -yert of 75 was achieved.

Example 6

The viscose was produced as indicated in Example 1, but instead of Marlox FK 64 the mercerising liquor contained 10 g per liter or 25 ^{% of} the weight of the alpha cellulose, piperidine. The viscose contained 5.4 1 ° NaOH and 9.5 % cellulose, the falling ball viscosity was 60 seconds. A viscose KW value of 69 was achieved.

Example 7

The viscose was produced as indicated in Example 1, but instead of Marlox FK 64, the mercerising liquor contained 10 g per liter or 25 ° ß> by weight of the alpha cellulose, those polyethylene oxide-polypropylene oxide copolymers whose trade name is Genapol PF 10, and their The manufacturer of Farbwerke Hoechst AG is. The viscose contained 5.1 ^J A NaOH and 9.8; ^; o Cellulose, the falling ball viscosity was 4? Seconds. A viscose KW-V / crt of 37 was achieved.

Example 8

The viscose was produced as indicated in Example 1, but instead of Marlox it contained FK 64 (Me neraorirjicrlauijü 10, <* per liter or? 5;. 'From G!) V / ic!) !; dor Alph'ix.ollul-O.je, such äthoxyli orte Fettamino, Loron trade name Berol / iüco ⁷ P. is, and that of Berol. Kemi AB manufactured. The '/ iskose contained 4,8' TIaOlI and 9, B, J cellulose, the ball fall vislcojü did M seconds. A Vislcoje KW value of 61 was achieved.

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BATH ORIGINAL

Example 9

The viscose was produced as indicated in Example 1, but instead of Marlox FK 64, the Merzcri.Jierlauge contained 0.2 g / l or 0.50 ! » the alpha cellulose, those ethoxylated oleylamines whose trade is Genamin 0-020, and their manufacturers

Farbwerke Hoechst AG is. The viscose contained 5.4 % NaOH and 9.6% cellulose, the ball viscosity was 57 seconds. A viscose K './- V / ert of 50 was achieved.

Example 10 Example 11 Example 12

The viscose was prepared as indicated in Example 1, but instead of Marlox FK 64 contained the Merzer irsierlauge 10 g / l or 25. '' Of the alpha cellulose quantity Ha-Saiz the sulfonated alkyl ester whose trade name Berol VMA is 478, and its Manufacturer Berol Kenii AB is. The viscose contained 5.2 ^r / o NaOH and 9.7 * cellulose that Kugelfallviskosi did was 43 seconds. The viscose KVM / ert was 19.

The viscose was prepared as indicated in Example 1, but instead of Marlox FK 64 contained the Merzerisierlauge 10 grams per liter or 25 '/ <> of the alpha cellulose amount such alkylene oxide-alkylphenol-Ädditionsprodukt whose trade name Marlox NP 109 is untl whose Manufacturer Chemische Werke Hüls AG is. The viscose contained 5.3 % NaOH and 10.4 % cellulose, the falling ball viscosity was 46 seconds. The KW value of the viscose was 59.

The viscose was prepared as indicated in Example 1, but instead of Marlox FK 64, the Merzerisierlauge contained 0.1 g per liter or 0.25 Ά of the alpha cellulose quantity, technical soya lecithin, whose fat content is fi 35th The viscose contained 5.0 / 6 NaOH and 9.5 "/» cellulose, the ball falling visco si did

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1 ^ 710309

was 23 seconds.

A viscose KW value of 47 was

Example 13

For a comparative viscosity produced in the same way, but without lecithin, the KW value was 2000.

Made from an ordinary, bleached 3irkenoulfatzellstoff, which is used by the paper industry, the alpha cellulose content of approx. 8? / o is an Vis-cose was prepared according to Example 1, but instead of Marlox FK 64 contained the Merzerisiorlauge 10 grams per liter or 25 'f ° from the alpha cellulose amount of methyl isobutyl ketone. The viscose contained 5.1.7 ° NaOH and 9.4 % cellulose, the falling ball viscosity was 20 seconds. A viscose KW value of 60 was achieved.

For a comparative viscosity prepared in the same way, but without methyl isobutyl ketone, the value was KW-tfert 1024.

₍ Example 14

Example 15

The viscose was produced as indicated in Example 13, but instead of methyl isobutyl ketone, the mercerising liquor contained 10 g per liter or 25 # of the amount of alpha cellulose, a mixture of technical primary amyl alcohol isomer made by Union Carbide Chemicals Co. and which contains 60 / pentanol-1 and 40 ·; ί 2- and 3-methylbutanol-1. The viscose contained 4.5 1 "NaOH and 9.4 '% cellulose, falling ball viscosity was 13 seconds. A viscose KW value of 49 was achieved.

Ordinary, bleached pine sulphate pulp, which the paper industry uses and whose alpha cellulose content was approx. 87 "ß> , became with mercerising liquor

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Αϊ

a 4.5 liter suspension, deron concentration 225 g

NaOH per liter, was the Hemizelluloaegehalt was 32 g / l and the temperature mercerized +55 ⁰ C in 50 minutes. The mercerising liquor also contained 0.2 s / l or 0.50 · / l of the amount of alpha cellulose, technical grade soy lecithin, the fat content of which was removed by extraction with acetone. The alkali cellulose was pressed, pre-ripened and, as indicated in Example 1, sulfided. The viscose contained 5.3 "p NaOH and 9.6 ] Ό cellulose with a falling ball viscosity of 37 seconds. The KV / -V / ert of the viscose was 82.

Example 16 Softwood sulfite dissolving pulp in 10 minutes to a 4 / ί-term suspension mercerized whose concentration was using a Merzerisierlauge 225 g NaOH per liter, temperature of +25 ⁰ C, and 0.1 g per liter or 25 ';& from the amount of alpha cellulose, containing technical grade soy lecithin. As indicated in Example 1, alkali cellulose was produced from the suspension. The alkali cellulose was after the preripening with Schwefelkohlenotoff, 25, "the weight of the Alphazellulo3e, sulfided UNU the xanthate was dissolved to a viscose containing 5.1 f '' 60 NaOH and 9.6 Ί" alpha cellulose contained, and the falling ball viscosity Seconds. The KW value of the viscose was 58.

In the case of a comparative viscosity produced in the same way, but without lecithin in the mercerising liquor, the KW value was 283.

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Claims (5)

Applicant: Kemira Oy Malminkatu 30, SF-00101 Helsinki 10, Pinnland Patent claims: , 1. / experienced in the production of alkali cellulose from ν - ^y cellulosic starting material, in which reached is that the raw material reacts with the mercerising liquor, characterized in that the raw material used is cellulose which was produced by alkaline cooking, without prehydrolysis and / or acidic cooking, without alkali upgrading, the cellulose, the mercerising liquor and / or the alkali cellulose at least an organic compound is added, such as alcohol, ester, ether, ketone, amine, acid or its Na salt, imine or aliphatic hydrocarbon containing at least 4 carbon atoms. 2. The method according to claim 1, characterized in that, based on the amount of alpha cellulose, 0.1-100% organic ether, Ester, ketone, amine, acid or their sodium salt, alcohol and / or pyridine derivative is added. 3. The method according to claim 1, characterized in that, based on the amount of alpha cellulose, 0.01-20 % phosphatidylcholine, phosphatidylethanolamine, inositol phosphatide, sugar, sterols, fatty acids, triglycerides or a mixture thereof such as lecithin is added. 4. The method according to any one of claims 1 to 3t characterized in that an organic compound that sees at least one hydrophobic, at least 3 carbon contains atoms containing aliphatic chain, and contains at least one hydrophilic group, added will. 5. The method according to any one of claims 1 to 4, characterized in that an organic compound in which a polyoxyethylene or polyoxypropylene group or Groups contain ice that is added. 709837/0334