FI69654B - FOERFARANDE FOER DELIGNIFIERING AV LIGNOCELLULOSAMATERIAL - Google Patents

Description

1 69654

This invention relates to a method for removing lignin from a lignocellulosic material, such as wood, straw, reed, bagasse, hemp, etc., using a chemical process. The process is characterized in that the cooking is carried out in a bath ratio of 1: 3 to 1:50 in the presence of a thioamide, thiourea, thiocarbamate or dithiocarbamate compound 10.

Suitable thiourea and dithiocarbamate compounds are both cyclic and preferably acyclic compounds. Among these, acyclic thiourea compounds are highly preferred. Preferred compounds to be used are the compounds R1 of the formula (1)

(1) ^ N - C - X

X »R 2 s wherein X is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, XR 3 to N, -OM or -SM, and each of R 1, R 2, R 1 and R 2 may be independently be hydrogen, alkyl of 1 to 12 carbon atoms, lower alkoxy-lower alkyl, phenyl, benzyl or phenyl or benzyl substituted by halogen, lower alkyl, lower alkoxy, alerapi-alkoxy-lower alkyl or sulfo or substituents (R 1 and R 2) and (R 3 and R 1) independently of one another together with the 2 69654 nitrogen atoms to which they are attached form a five- or six-membered heterocyclic group or and together form an alkylene or phenylene having 2 to 3 carbon atoms and M is a cation.

In the groups of the compounds of formula (1) and in the following formulas, lower alkyl and lower alkoxy generally mean groups or parts of groups having 1 to 5, in particular 1 to 3, carbon atoms, such as, for example, methyl, ethyl, n- a propyl, isopropyl, n-butyl, tert-butyl, 10-sec-butyl or amyl group or a methoxy, ethoxy or iso-propoxy group. Halogen may be, for example, fluorine, bromine or, preferably, chlorine.

The term "sulfo" means a sulfonic acid group. Aryl means in particular phenyl and aralkyl in particular benzyl.

If the substituents X, R 1, R 2, R 3 and R 2 represent an alkyl group, this may be straight-chain or branched.

These alkyl groups may contain 1 to 12, preferably 1 to 5 and most preferably 1 to 3 carbon atoms. Such alkyl radicals are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl or n-dodecyl.

If the substituents R., R ", R-, and R. denote a lower p-alkoxy-lower alkyl group, it is primarily alkoxyalkyl having a total of 2 to 4 carbon atoms, such as β-methoxyethyl or β- ethoxyethyl.

Examples of cycloalkyl groups X are cyclopentyl or preferably cyclohexyl.

When the group X represents aralkyl, it is usually phenylethyl or especially benzyl, while aryl preferably means naphthyl, diphenyl and, above all, phenyl. Aralkyl groups and aryl radicals may be substituted by halogen, lower alkyl, lower alkoxy or sulfo.

Preferred substituents on the phenyl or benzyl group of the radicals X and R are, for example, halogen, lower alkyl or lower alkoxy, such as chlorine, methyl or methoxy.

tl 3 6 Γ · 6 5 4

If the substituent pairs (R 1 and R 2) and (R 8 and R 2) together with the nitrogen atom to which they are attached form a heterocyclic group, this group may be, for example, pyrrolidino, piperidino, pipecolino, morpholino or thiomorpholino.

When R 1 and R 8 together represent alkyl having 2-3 carbon atoms, they together with the nitrogen atom connecting them form a cyclic thiourea compound such as ethylene thiourea or propylene thiourea. When R 1 and R 8 together represent phenylene, they together with the thio-10 ureido group form a phenylene thiourea which may be substituted with R 2 and R 2. Thiouracil-2 can also be used as the cyclic thiourea compound.

The preferred substituent X is a lower alkyl or especially RgR1N group. Preferred groups R 1, R 8, R 8 and R 2 are hydrogen or in each case lower alkyl groups, such as methyl or ethyl.

The cation M can be, for example, hydrogen, an alkali metal, in particular sodium or potassium, an alkaline earth metal, in particular magnesium or calcium or an ammonium group. As used herein, the term "ammonium group" refers to an ammonium group (NH 2+) as well as substituted ammonium groups.

The latter are due, for example, to aliphatic amines, such as di- or triethyl or mono-, di- or triethanolamine, or cycloaliphatic amines, such as cyclohexylamine. Preferred groups M are hydrogen, alkali metal or ammonium.

According to the invention, it is preferred to use the compounds of formula (2) R5

(2) ^ N - C - X

r / S

S * 1 wherein X 1 is lower alkyl or the group -N and each group

Vr8 30 wherein R1, R8, R2 and R8 may each independently be hydrogen or lower alkyl. In addition, the group X 1 may preferably be phenyl.

Among the compounds of formula (2), highly preferred are those in which X 1 is methyl, NH 2 or 5 -N (CH 1) 2 3a R 5 and R 8 represent hydrogen or methyl. Typical representatives are thioacetamide, thiobenzamide, tetramethylthiourea and above all thiourea.

Also very suitable are dithiocarbamates of the formula (3) R1 (3), N-C-S-M,

R2 S

10 wherein and R 2 are as defined above and are alkali metal or ammonium.

In the compounds of formula (3), R 1 and R 2 preferably represent lower alkyl, such as methyl or ethyl. The most important representative of this group of compounds is sodium diethyldithio-15 carbamate. Other thiocrabamates are, for example, piperidine sodium dithiocarbamate or diethylammonium diethyldithiocarbamate.

According to the invention, the compounds of the formulas (1) to (3) are used primarily as additives when it is desired to separate cellulose from lignocellulosic materials so that satisfactory cellulose yields are obtained at a given kappa number (TAPPI method T-236 M-60).

The compounds of the formulas (1) to (3) are added to the pulp solutions from 0.001 to 5% by weight, preferably from 0.001 to 2.5% by weight, based on the lignocellulosic material.

Said thioamines, thioureas, thiocarbamates and dithiocarbamates are used alone or preferably in combination with an organic, cyclic compound containing keto and / or hydroxy groups.

30 Suitable organic, cyclic compounds containing keto and / or hydroxy groups are, for example, mono-,

II

5 69654 di- and / or polycyclic and in particular di-, tria- and / or tetracyclic compounds containing two keto groups and / or two hydroxy groups. These are, in particular, 1,4-naphthoquinone, 9,10-anthraquinone, Diels-5 Alder adducts of 1,3-dienes, e.g. p-benzoquinone and / or 1,4-naphthoquinone adducts of unsubstituted or substituted butadiene, and / or or their monoalkyl, dialkyl, hydroxy, amino, alkoxy, alkylamino, halogen and / or sulfo derivatives.

According to the invention, 9,10-ant-10 rhininone, 2-methylanthraquinone, 2-ethylanthraquinone, dichloroanthraquinone, 2,3-dimethylanthraquinone, 2,6-dimethylanthraquinone, 2,7-dimethylanthraquinone, 2-aminoanthraquinone can be used. nia, 1-methoxyanthraquinone, 2-methoxyanthraquinone, anthraquinone-2-sulfonic acid or anthraquinone disulfonic acid (as alkali metal salts), 1,2-benzanthraquinone, phenanthrene quinone, anthrone, 10-methyleneanthrone, dihydroxyanthracenene, dihydroxy 9,10-di-ketoanthracene or 1,3-dimethyl-tetrahydro-9,10-diketo-anthracene. According to the invention, two or more of these keto compounds can be used. Preferably only one of these compounds is used and it is quite suitable to use 9,10-anthraquinone or 2-methyl-9,10-anthraquinone with said thioamides, thioureas or dithiocarbamates.

According to the invention, it is possible to use mixtures which contain, for example, 50 to 95% by weight of one or more compounds containing organic, cyclic, keto and / or hydroxy groups, in particular 9,10-anthraquinone, and 5 to 50% by weight of one or more a compound of formulas (1) to (3). Preference is given to mixtures containing 60 or preferably 70 to 90% by weight of a cyclic compound containing keto and / or hydroxy groups, in particular 9,10-anthraquinone or 2-methylanthraquinone, and 10 to 40, preferably 10 to 30 by weight% of a compound of formulas (1) to (3), preferably thiourea, thioacetamide, tetramethylthiourea or sodium diethyldithiocarbamate.

Mixtures of thiourea and anthraquinone in a mixture ratio of 1: 3 or 1: 4 or preferably between 1: 9-6 6 9 6 5 4 3: 7 are very suitable.

Mixtures of compounds of the formulas (1) to (3) and cyclic keto and / or hydroxy compounds are added to the pulp solutions from 0.001 to 1% by weight, preferably from 0.001 to 0.2% by weight, based on the lignocellulosic material.

The lignocellulosic material used is mainly wood. This is usually done first with chips or shavings.

The wood can be softwood such as balsam pine, spruce or larch, or hardwood such as maple, birch, beech, 10 oak, aspen or poplar. The lignocellulosic material may also be in fibrous form.

The chemical cooking for the purpose of separating the cellulose preferably takes place in a basic medium, e.g. by the sulphate or kraft method, the soda cooking method, the sulphite method under semi-basic conditions or the so-called oxygen-alkali method. In the latter case, oxygen may be added before, during or after the alkali treatment. Another cooking method for recovering cellulose according to the invention is the polysulphide method. This can be done both alkaline and neutrally. The neutral sulphite cooking method can be applied in particular when using said mixtures of thio compounds and cyclic keto compounds. Further, the lignocellulosic material may be treated by boiling in the first cooking step in the presence of sodium hydroxide, defibrating the treated material and treating the defibered material in a second cooking step performed in the presence of a peroxide such as hydrogen peroxide, alkaline solution or alkali peroxide.

The cooking according to the invention can be carried out at a temperature between 50 and 250 ° C, preferably between 120 and 200 ° C. The cooking takes place in a bath ratio in which the ratio of the amount of lignocellulosic material to the pulp solvent is between 1: 3 and 1:50, preferably between 1: 3 and 1:10.

The lignocellulosic material is preferably treated in a closed container in a bath ratio of 1: 3 to 1:10 with alkaline

II

7 69654 with a mixture containing 0.001 to 0.2% by weight of a mixture of a compound of formulas (1) to (3) and an anthraquinone compound based on the ligno-cellulosic material. Sodium hydroxide and / or magnesium hydroxide in the form of a 2-15% aqueous solution is preferably used as the alkali. Very good results are also obtained by combining said sodium hydroxide solution and sodium sulfide in the so-called according to the sulphate method. Sodium sulfide is preferably used in an amount of 0.01 to 40 g / l, more preferably 0.1 to 25 g / l.

Instead of using anthraquinone alone as a known lignin remover, the process according to the invention, in particular by using said mixture, gives wood pulps which produce papers with better strength properties. In particular, due to the synergistic effect of the mixture 15 used, it is possible to reduce the amount of the expensive anthraquinone derivative while keeping the yield and the non-fibrous removal rate practically unchanged.

In the following examples, the chlorine number represents a measure of lignin-20 residue and yield. Percentages are percentages by weight and parts by weight. Atro means absolutely dry.

Examples 1-3: Three batches of 25 g of wood chips (Picea

Abies, maximum thickness 3 mm) is placed in an autoclave, 100 ml of 1.18 N aqueous sodium hydroxide solution are added at 80 ° C and purged with nitrogen. The mixture of thiourea and 9,10-anthraquinone (Table 2) to be examined in Table 1 below is then added to each alkaline mixture in the given percentage (column 3) and mixture ratio (column 4), then the temperature is raised to 173 ° C and the boil is kept at 2 hours at this temperature. The mixtures are cooled, crude. filtered and washed with hot water and deionized water. The pulps are then defibered and compressed into sheets. Finally, the average chlorine numbers and 8 69654 average yields of the three experiments of each of the 35 examples are determined. The results obtained are summarized in Table 1. The mass yield, calculated as a percentage by weight of the wood used, is shown in the last column of the table. The lignin content of the pulps is calculated by multiplying the chlorine consumption by a factor of 0.90 according to the method "Scandinavian pulp, paper and board testing comit§, (Scan-C 29:72)". The corresponding chlorine numbers are shown in column 5 of the table. The carbohydrate content of the pulps is the difference between the pulp yield and the lignin content. The last column of Table 10 shows the yield of lignin-free cellulose.

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Examples 4-6: In each case, three batches of 25 g of wood chips are placed in an autoclave, 100 ml of 1.11 N aqueous sodium hydroxide solution and 1.13 g of sodium sulfide are added at 80 ° C and purged with nitrogen. The mixture of thioure and 9,10-anthraquinone to be tested in Table 2 below (column 2) is then added to each alkaline mixture in a given percentage (column 3) and mixture ratio (column 4), then the temperature is raised to 168 ° C and kept for 2 hours at this temperature. The mixtures are cooled, the crude masses are collected and washed with hot water and rinsed with deionized water. The pulps are then defibered and compressed into sheets. Finally, the average chlorine numbers and average yields obtained from the experiment of each individual example are determined. The results are summarized in Table 2. Chlorine numbers are shown in column 5 of the table, and columns 6 and 7 show pulp yields and yields of lignin-free cellulose as a percentage of the amount of wood used.

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Examples 7-9: In each case, three 25 g batches of wood chips are placed in an autoclave, 100 ml of 1N aqueous sodium hydroxide solution and 2 g of sodium sulfide are added at 80 ° C and purged with nitrogen. To each alkaline mixture is then added the test mixture of thioure and 9,10-anthraquinone listed in Table 3 below (column 2) in a given percentage (column 3) and mixture ratio (column 4), then the temperature is raised to 168 ° C and maintained at this temperature for 2 hours. The mixtures are cooled, the crude masses are collected and washed with hot water and rinsed with deionized water. The pulps are then defibered and compressed into sheets. Finally, the average chlorine numbers and average yields obtained from the three experiments in each individual example are determined. The results are summarized in Table 3. The chlorine figures are shown in column 5 of the table and columns 6 and 7 show the pulp yields and lignin-free cellulose yields as a percentage of the amount of wood used.

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λ; Ή I Ai • HP Γ 'oo σ w ω w ε 14 6965 4

Example 10; In each case, three 25 g batches of wood chips are placed in an autoclave, 100 ml of 1.18 N aqueous sodium hydroxide solution are added at 80 ° C and purged with nitrogen. Thiourea or 9.10 anthra-5 quinone (column 2) is then added to each alkaline mixture with the given percentages or operated without additive, then the temperature is raised to 173 ° C and the boiling is kept at this temperature for 2 hours. The mixtures are cooled, the crude masses are filtered and washed with hot water and rinsed with deionized water. The mas-10 sat is then defibered and compressed into sheets. Finally, the chlorine numbers and average yields obtained from the three experiments in each individual example are determined. The results are summarized in Table 4. The chlorine numbers are shown in column 3 of the table, and columns 4 and 5 show the yields of pulp-15 and the yields of lignin-free cellulose as a percentage of the amount of wood used.

As can be seen from Example 10, thiourea can also be used alone to increase the selectivity of the process. However, about 40 times 20 times more thiourea than anthraquinone is needed to achieve the same effect. The fact that a mixture of up to 30% thiourea and 70% anthraquinone produces the same effect as anthraquinone alone (cf. Examples 1-9) indicates that this additive combination has a synergistic effect.

69654 15

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Examples 11-20; In each case, two batches of 25 g of wood chips are placed in an autoclave, 100 ml of 1.118 N or 1.23 N aqueous sodium hydroxide solution are added at 80 ° C and purged with nitrogen. Anthra-5 quinone, tetramethylthiourea, ethylenethiourea, benzothioamide or sodium diethyldithiocarbamate is then added to each alkaline mixture or operated without additive (Table 5, column 3) and the temperature is raised to 173 ° C where the boils are kept for 2 hours. The mixtures are filtered and the crude masses are washed with hot water and rinsed with deionized water. The pulps are then defibered and compressed into sheets. The chlorine numbers and yields of the individual experiments are then determined and the averages of the two corresponding experiments are calculated. The results are summarized in Table 5. The chlorine numbers are shown in column 5 of Table 15 and columns 6 and 7 show the pulp yields and the yields of lignin-free cellulose as a percentage of the amount of wood used.

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6965 4

Examples 21-35: In each case, two 25 g batches of wood chips are placed in an autoclave, 100 ml of 1.116 N or 1.126 N aqueous sodium hydroxide solution are added at 80 ° C and purged with nitrogen. Anthra-5 quinone, ethylenethiourea, thioacetamide or thiouracil-2 (Table 6, column 3) is then added to each alkaline mixture and the temperature is raised to 173 ° C where the boils are kept for 2 hours. The mixtures are cooled, the crude masses are filtered off and washed with hot water and rinsed with deionized water. The pulps are then fibrous-10 and compressed into sheets. The chlorine numbers and yields of the individual experiments are then determined and the averages of the two corresponding experiments are calculated. The results are summarized in Table 6. The chlorine numbers are shown in column 5 and columns 6 and 7 show the pulp yields and the yields of lignin-free cellulose as a percentage of the amount of wood used.

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2o 69654

Examples 36-41: In each case, three 25 g batches of wood chips are placed in an autoclave, 100 ml of 1.10 N aqueous sodium hydroxide solution (in Examples 39-41 still 11 g / l Na2S) are added at 80 [deg.] C. and purged with nitrogen. Anthraquinone, 2-methylanthraquinone, thiourea, a mixture of thiourea and 2-methylanthraquinone (1: 4), a mixture of thiourea and anthraquinone (1: 3) or a mixture of thioacetamide and anthraquinone (1: 3) are then added to each alkaline mixture. ) (Table 7, column 3) and the temperature is raised to 173 ° C (Examples 39-41: 168 ° C), where the decoctions are kept for 2 hours (Examples 39-41: 53 minutes). The mixtures are then cooled, the crude masses are filtered off and washed with hot water and rinsed with deionized water. The pulps are then defibered and compressed into sheets. The chlorine numbers and yields of the individual experiments are then determined and the averages of the three corresponding experiments are calculated. The results are summarized in Table 7. The chlorine numbers are shown in column 5 and columns 6 and 7 show the pulp yields and the yields of lignin-free cellulose as a percentage of the amount of wood used.

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Examples 42-53: In each case, three batches of 25 g of wood chips are placed in an autoclave, at 80 [deg.] C. 100 ml of a 1.10 N aqueous sodium hydroxide solution are added (in Examples 46-49 a further 11 g / l Na2S, in Examples 50-53 a further 40 g). , 6 g / l Na 2 S) and huuh-5 is purged with nitrogen. Anthraquinone, thiourea or a mixture of thiourea and anthraquinone (1: 3) (Table 8, column 3) is then added to each alkaline mixture and the temperature is raised to 160 ° C (in Examples 46 to 53 to 150 ° C) where the boils are kept for 90 minutes. (Examples 46-53 for 45 minutes).

The mixtures are then cooled, the crude masses are filtered off and washed with hot water and rinsed with deionized water. Next, the pulps are defibered and compressed into sheets. The chlorine numbers and yields of the individual experiments are then determined and the averages of the three corresponding experiments are calculated. The results are summarized in Table 8. The chlorine numbers are shown in column 5 and columns 6 and 7 show the pulp yields and the yields of lignin-free cellulose as a percentage of the amount of wood used.

In addition, part of the raw pulp is bleached and the viscosity of the cellulose is determined. The values obtained are shown in column 8 of the table.

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Examples 54-57: At 80 [deg.] C., 700 g (Atro) of spruce chips (picea excelsa) and 2.8 l of cooking liquor are in each case placed in an autoclave. The composition of the cooking liquor is shown in Table 9. The mixtures are heated at a rate of 1 ° C / min to 5,173 ° C (Examples 54-56) or 168 ° C (Example 57) where they are kept for 2 hours (Examples 54-56) or 1 hour (Example 57). The mixtures are cooled and the resulting celluloses are processed and analyzed in the usual way. The results are shown in Table 9. The celluloses are then ground to 10 (each with 6 different degrees of grinding) and the corresponding physical properties are determined. The results are summarized in Tables 10 to 13, and the tear values and corresponding tear lengths are also given for comparison purposes.

From the tear values and the corresponding tear lengths 15, it can be seen that the celluloses of Examples 54 and 55 have approximately similar strength properties, although the kappa number is slightly higher in Example 55. In addition, it is found that the separated yield in Example 55 is about 3.7% higher. From the difference in lignin-free yields (2.6%) 20, it can be concluded that this higher yield is due to the higher carbohydrate yield. The coarse mass yield in Example 55 is slightly better than in Example 54. The viscosity is also better.

Comparing the tear values to the corresponding tear lengths in Examples 54 and 57 (sulfate method, 20% sulfidity), the following can be observed: The strength properties of cellulose cooked with thiourea are slightly better than those cooked with anthraquinone, although the lignin content is better. This is also compatible with a higher vis-30 cosity; the yield is better. The strength properties, viscosity and lignin-free cellulose yield in Example 56 are comparable to those of the cellulose obtained by the sulphate process described in Example 57 (sulphidity about 20%), although the corresponding sulphidity is only half (about 10%) when administered via thiourea.

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Comparative Example

In each case, two batches of wood chips (Picea Abies), 25 g each, are placed in an autoclave, 100 ml of aqueous 1.1 N sodium hydroxide solution are added at 80 ° C. Then add to each alkaline mixture thiourea or vast, thiourea dioxide or vast, sodium dithionite, which is added in the following table, the percentages shown in column 2, after which the temperature is raised to 173 ° C over 90 minutes and the resulting mixture is kept 1 3/4 hours at this temperature. After cooling, the crude mass is filtered off, washed with hot water and rinsed with deionized water. The pulps are then defibered and compressed into sheets. Finally, the chlorine numbers and yields of the individual experiments are determined and the averages of the two corresponding experiments are calculated. The results are summarized in Table 14. The chlorine numbers are shown in column 3 and columns 4 and 5 show the pulp yields and the yields of lignin-free cellulose as a percentage of the amount of wood used.

Table 14 1_2_3_4_5_

Additive% amount chlorine number mass yield% lignin-free cellulose yield% without - 13.9 58.4 51.1 additive thiourea 1 9.1 56.1 51.5 thiourea 1 14.4 59.3 51 * 6 dioxide sodium di - 1 13.5 58.4 51.3 thionite_li

Claims (15)

A process for delignifying lignocellulosic materials by boiling, characterized in that the boiling ratio of 1: 3 - 1:50 is used in the presence of a thioamide, thiourea, thiocarbamate or dithiocarbamate compound. Process according to Claim 1, characterized in that cyclic or acyclic thiourea or dithiocarbamate compounds are used. 10 3. A process according to claim 1 or 2, characterized in that an acyclic thiourea compound is used. 4. A process according to claim 1, characterized in that a compound of formula (1) R1 (1) is used. N - C - X / II r aralkyl, R 3 - N, -OM or -SM, R 4 R 4 lower alkyl, lower alkoxy, lower alkoxy lower alkyl or sulfo substituted phenyl or benzyl or the substituent pairs (R 2 and R 2) and (R 2 and R 2) can independently form one or five heterocyclic residues with this nitrogen atom. members or R 2 and R 2 together form alkylene of 2-3 atoms or phenylene and M is a cation. Il 69654 Process according to claim 4, characterized in that a compound of formula (2) R5 (2) - C - X, / II VS XR7 is used which is lower alkyl or - N and R ? and R 9 may be independently hydrogen or lower alkyl. 6. A process according to claim 4, characterized in that a compound of the formula (3) R 1 (3) N - C - S - NL / n 1 r / s is used where R hydrogen, alkyl of 1 to 12 carbon atoms, lower alkoxy-lower alkyl, phenyl, benzyl or with halogen, lower alkyl, lower alkoxy, lower alkoxy-lower alkyl or sulfo-substituted phenyl or benzyl or R 2 and R having five or six members and is an alkali metal or ammonium group. 7. A process according to claim 6, characterized in that a compound of formula (3) is used, wherein R 1 and R 2 are lower alkyl. 8. A process according to claim 1, characterized in that an organic, cyclic, keto and / or hydroxy groups containing compound are used together with the thioamide, thiourea, thiocarbamate or dithiocarbamate compound. 9. A process according to claim 8, characterized in that the additive compound is a di-