CA1040216A - Production of syringealdehyde and/or vanillin from hardwood waste pulping liquors - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Syringealdehyde is produced from alkaline and neutral sulphite waste liquors by alkaline oxidative treatment of the liquor and subsequent isolation and purification of the aldehyde.

Description

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FIEL~ OF THE INVENTION
The present invention relates to the production of organic aldehydes from waste pulping liquor. It is concern-ed, more particularly, with a process for making syringeal-dehyde and/or vanillin by alkaline oxidative treatment of waste liquor from alkaline and neutral sulfite pulping operations.
DESCRIPTION OF THE PRIOR ART
There is no commercial production of syringealde-hyde, as far as we know. There are known methods of pre-paring syringealdehyde by synthetic routes, e.g. through several intermediate reactions starting from pyrogallol as disclosed in U.S. Patent 2,516,412, or from vanillin by selective methylation of the 5-hydroxyvanillin derivative (J. Am. Chem. Soc. 74, 4262, 1952~. These methods how-ever do not lend themselves to commercial use, and only minute quantities of syringealdehyde have been available in the trade. The potential demand for syringealdehyde, however, has greatly increased, primarily in connection with its usefulness for the production of 3,4,5-trimethoxy-benzaldehyde, itself an important drug intermediate.
It is known to produce vanillin from lignin re-s$dues obtained from the digestion of wood to cellulosic pulps and a number of commercial processes of this type for the production of vanillin have been in existence for many years. All these processes, however, are based on the processing of lignin from spent sulfite liquor in which the lignin residue is in the form of lignosulfonate. To the best of our knowledge, vanillin has never been produced on a commercial scale from alkaline waste pulping liquors, such as Kraft black liquor.
Vanillin produced by the above processes using

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an oxidative breakdown of liynin i.n spent sulfite li.quors is often accornpanied by syringealdehyde. The quantities of syringealdehyde thus appearing as an impurity vary from very small in the case of lignin originating from coniferous woods to substantial in the case of lignin from pulping de-ciduous woods.
BRIEF DESCRIPTION OF THE INVENTION
A process for the production of syringealdehyde from a lignin containing waste liquor of a hardwood alkaline or neutral sulfite pulping operation comprising: forming a charge of the waste liquor and alkali, passing oxygen containing gas in intimate contact with the charge in a reactor to oxidize said liquor, neutralizing the oxidized liquor, extracting the neutralized oxidized liquor with an organic solvent thereby to separate an organic solvent soluble fraction containing lignin derived aldehydes and an aqueous fraction containing residual lignin and inorganic chemicals, treating the organic solvent soluble fraction with an aqueous solution of sodium bisulfite to form from part of the organic solvent soluble fraction an aqueous solution of a sodium bisulfite complex of syringealdehyde and vanillin, separating the aqueous solution .: `
of the complex from the remainder of the organic solvent soluble fraction, acidifying the aqueous solution to recover a mixture of syringealdehyde and vanillin, separating syringe-aldehyde from vanillin.
The single Figure of the drawing is a schematic re-presentation of the sequence of steps in the present process including the several cycles of recovery and reuse of the :
chemicals used at various stages.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The starting material in the process of the invention ..
is a waste liquor from an alkaline or neutral hardwood pulping .

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.-pulping operation, e.g. a Kraft black liquor, or a residualliquor from a soda cook or from a neutral sulfite semi-chemical cook. Spent liquors from sulfite pulping - 3a -~ - - . .. . ...

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operations are also suitable, however such Iiquors have now become less widely available because of the relative decline of the sulfite process. While in the present description reference is made particularly to conventional Kraft liquor, it will be understood that the process may also be used with waste liquors from modified Kraft processes, such as vapour phase Kraft, polysulfide, etc., as well as with other waste liquor as hereinabove stated.
In the normal operation of a Kraft mill, the black liquor collected after separation and washing of the pulp is concentrated by evaporation, e.g. in a multiple effect evaporator, and the concentrated liquor is burnt in a re-covery furnace. The combustion of the organic constituents of the liquor provides valuable quantities of heat, e.g for steam production, while the inorganic constituents col-lect in the form of a smelt which is recovered and processed back to a composition identical with that of the initial pulping liquor. In accordance with the invention, at least a portion of the black liquor is transferred to a reactor in the aldehyde plant. The liquor to be processed may be withdrawn from the stream of black liquor on the way to recovery, or, in a particular embodiment of the inven-tion, a portion of the cooking liquor may be withdrawn from the digester before the end of the cook.
We have found that there is an advantage in the latter procedure, since with exposure to elevated tempera- ~ ;
ture for an extended time the lignin in the liquor becomes less susceptible to conversion to the desired aldehydes.
Naturally, if the latter procedure is used, only a certain percentage of the liquor can be withdrawn from the digester without affecting the yield or quality of the pulp, but it `
has been found that up to a third of the liquor can be withdrawn from the digester without ill effects. The best .
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1040Z~i time for such withdrawal may have to be de~ernlirled lor particular cook schedules, keeping in mind that in the early stages of the cook the lignin will be highly reactive and convertible to the desired aldehydes at a high yield, but the quantity of lignin dissolved out of the wood wi]l be relatively small, while with the passage of time the quantity of lignin dissolved out will increase but some of the lignin will have undergone thermolytic changes which make it less susceptible to conversion. Since the two tendencies will exist simultaneously, the optimum for any particular cook schedule, species, etc., will best be found experimentally with the help of a few simple measurements on samples of the liquor during the cook.
For the purpose of this process it is preferred to use the black liquor in a partly concentrated condition, e.g. at a concentration of about 25-35% solids. Alkali, such as caustic soda, is added to this liquor in the reactor, so that the ratio of alkali to lignin present in the liquor to be treated is about 0.5 - 3 parts alkali to 1 part lignin on a weight basis. The oxidation is carried out in a known manner by passing air through the alkaline solution at a temperature above 100 C, preferably 140 - 180 C, under pressure of about 50 to 150 psig. A catalyst may be used to increase the yield of aldehyde, such catalyst consisting essentially of a salt of a transition metal capable of readily existing in more than one oxidation stage. Examples of such catalyst are salts of copper, manganese, nickel, iron and cobalt. The oxidation is continued until the yield of syringealdehyde and vanillin has reached a maximum which is generally indicated by a drop in the pH of the solution or a drop in its temperature (in the absence of external heating), or can otherwise be determined in a simple test for aldehyde content.

- ~ -.: . ~ ' ' ~ ~ ' 104~)Z16 As illustrlted in -the drclwing, the oxidiz~d alka-line liquor is neutralized. This can be done, e.g., by car-bonation in a suitable vessel, the carbonation being prefer-ably carried out in two stages: in a f`irst stage the oxi-dized liquor is contacted with scrubbed flue gas, e.g. in a packed tower, until the pH of the liquor is reduced to 9-9.5; and in a second stage the partially carbonated liquor is subjected to pressure carbonation, e.g. with C02 re-covered in the process, under pressure, until the pH of the solution is brought down as close to 7 as possible. Ob-viously the neutralization can be carried out by treatment with other acids as well, e.g. sulfuric acid. The neutralized solution is then subjected to an extraction with an organic solvent, e.g. benzene, toluene or the like, preferably at a temperature up to 80 C under pressure. The residual aqueous liquor remaining after extraction and containing residual lignin and substantial amounts of caustic is stripped of residues of the organic solvent and of residual C02, and returned to the pulp mill system for recovery of alkali values. The residual liquor may be added to the concen-trated black liquor going to the furnace, or to the "green liquor" in advance of the causticizing stage, depending on circumstances existing in the mill. For example, where the recovery furnace is already operating at capacity, it may be preferable to add the residual liquor to the green liquor, - .... : .. . .
but in normal circumstances it will be more advantageous to add it to the concentrated black liquor on the way to the furnace.
The organic extract containing the desired alde-hyde product is concentrated, the recovered solvent being returned for use in the extraction step, and the concen-trated solution is treated with an aqueous solution of sodium bisulfite to form a water-soluble sodium bisulfite . . .- . : : . : . - , . . : ~ .

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complex of syril~geLlldellydc ~Ind va~ irl. The ('()mr)leX i !i extracted and removed in the aqueous phase, whilc the or-ganic phase consisting primarily of the solvent (benzerle or toluene, or the like) is recovered, purified and return-ed for re-use in the solvent extraction step. Ihe aqueous extract is washed, e.g. with an alcohol, partially soluble in water, preferably an aliphatic alcohol having a chain of 4 - 6 carbons, to remove impurities, and then acidified with sulfuric acid to break up the complex and recover the mixture of aldehydes. The aldehyde mixture separates as a heavy oil which is washed, e.g. with water, to remove excess sulfuric acid, and the washed oil is transferred to further treat-ment or allowed to cool for storage. The wash water, to-gether with the aqueous phase from the acidification step (from which the S02 has been removed by heating), may berecycled, e.g. to the initial oxidized liquor, so as to minimize losses of the valuable aldehydes.
The crude aldehyde mixture is treated to separate the syringealdehyde from vanillin. It was found that such separation can be carried out successfully, contrary to es-tablished belief in the art, by fractional distillation, provided the mixture is substantially free of acid or al-kaline impurities. Hence the importance of the washing steps hereinbefore described. Syringealdehyde of a purity of 99.5% and vanillin of a purity of 99.9~ were obtained from the distillation. The products can be further purified by crystalization or other methods.
The process will be further described by means of the following examples which are provided to illustrate, but by no means to limit, the invention.
E mple 1 In a hardwood Kraft mill cook a portion of the liquor was withdrawn after 1.25 hours of pulping and evapor--: ., , - :
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104~)Z16 ated to 27.7% w/v (weight per v~lumd) totcll ~olid.s, (~1' wllich 8.48% was lignin and 2.30% free alkali. An oxidation charge was prepared consisting of 811 cu. ft. of this liquor, 80 cu.
ft. of 50% W/W (weight per weight) sodium hydroxide, 20 - 25 lbs ammonia-ted manganese sulfate and lO lbs of a defoamer, giving a mixture containing 7.72% W/V of lignin and a ratio of total free alkali to lignin 1.16:1. The mixture was oxidized by passing air through it at a temperature of 140 C, atla pressure of 70 psig, the air flow being about 15,000 cu.
ft. per hour.
Samples were taken at regular intervals and analyzed for syringealdehyde and vanillin (S-V) by gas-liquid chromato-graphy. The peak concentration of S+V was 0.439% W/V, reached in 6.5 hours and representing a yield on lignin of 5.69%. The S/V ratio was 2.04:1.
Liquor thus oxidized was treated to produce a crude - ~ -product, consisting of a mixture of syringealdehyde and vanil- -~
lin, by the following steps: the oxidized liquor was neu-tralized by carbonation in two stages, the neutralized liquor was extracted by means of benzene, the organic extract was concentrated and treated with an aqueous solution of sodium bisulfite to form a water-soluble aldehyde-bisulfite com-plex, the aqueous solution of the complex was separated from the organic phase and washed with amyl alcohol, and then treated with sulphuric acid. A heavy oil, consisting of a mixture of syringealdehyde and vanillin, was obtained. The oil was carefully washed with water and removed to storage.
Several samples of the crude product, of about 2 kg each, were subjected to fractional distillation in lab- -30 oratory apparatus under a vacuum of 120 - 175 microns.
Eight consecutive cuts were taken and analyzed by gas-liquid chromatography. In the temperature range 128 - 130C, (taken on the vapour) after a first cut of vanillin of a purity of 51040Z~6 98.5% and amounting to 3. of the charge, vclnillin Or ~1 purity 99.9% was collected totalling 35.1~ of the crude mix-ture. In the temperature range 170 - 172 C syringealdehyde was collected of a purity from 98.8% to 99.8%, totalling 36.1% of the mixture.
An intermediate fraction containing a mixture of vanillin and syringealdehyde and amounting to 12.4% of the charge was collected and recycled to the crude mixture for subsequent distillation. The fraction contained between 84.3% and 87.7% syringealdehyde and the remainder vanillin.
Example 2 Waste liquor from a conventional hardwood Kraft cook was evaporated to a total solids (TS) content of 53.7%
weight per volume (W/V) which included a lignin content of 11.8% W/V. The black liquor, water and 50% (W/W) sodium hydroxide were mixed in proportions such that the mixture contained 5% W/V of lignin and a ratio of added alkali to ~-lignin of 2:1. A quantity of 1500 ml of this mixture, to which were added 3.65 grams of the catalyst cupric sulfate pentahydrate, was placed in a one-gallon autoclave provided with suitable fittings for the addition and removal of samples and for the addition of air, and also fitted with heaters and a Cavitator stirrer operating at 1400 RPM. The mixture was oxidized by passing air through continuously at the rate of 7 litres per minutes, at a temperature of 165C
~- (which was reached in 1/2 hour) and at a pressure of 100 psig.
Samples were removed every 15 minutes and analyzed for syringealdehyde and vanillin (S+V) by gas-liquid chromato-graphy. Peak concentration of S+V in the oxidized liquor was reached after 1.5 hours. This concentration w~`s 0.396% - -W/V of S + V, representing a yield of S ~ V on lignin of 7.9%.
The syringealdehyde to vanillin ratio (S/V) was 2.19~
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Examples 3 - 6 104~Z16 Kraft waste liquor from a hardwood cook was pro-cessed substantially as in Example 2, except that some of the conditions such as temperature, pressure, lignin con-centration, alkali ratio, etc. in the reactor were changed from run to run. Also in some runs ammoniated manganese sulfate in an amount of 0.6g was used as catalyst. These : -conditions and the resulting yields of syringealdehyde and vanillin are set out below: -:' -10- , .', '', -:

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Example 7 104QZ16 This example illustrates further the u~e ~f early stage Kraft waste liquor, i.e. liquor removed from the digester before the completion of the cook. Such liquor was found to contain lignin in a form more amenable to conversion to S+V, but the lignin is in lower concentration than in a liquor withdrawn after completion of the cook. A sample of lignin was taken from the digester one hour after the start of steaming. It contained 22.7% total solids, of which 3.2%
lignin, and 1.69% free alkali as sodium hydroxide (all W/V).
The liquor was evaporated in the laboratory to 6%W/V lignin and after mixing with alkali and water the oxidation charge of 1500 ml contained 5% W/V of lignin, a ratio of toal alkali to lignin of 2.53:1, and a quantity of 3.65g of -cupric sulfate catalyst. The temperature of oxidation was 165C, the pressure 100 psig and the air flow was 7.0 litres per minute. The peak concentration of S+V, reached in 2.5 hours, was 0.597% W/V, representing a yield on lig- -nin of 11.94%. The S/V ratio was 2.43:1.
ExamDle 8 - 11 Early stage Kraft waste liquors, similar to the one used in Example 7, were used for the preparation of .. : .. .
syringealdehyde and vanillin substantially as described in -preceding examples with variations in the initial composi-tion of the liquor and in the conditions of the oxidation. ;
The liquors used were removed from the digester 1.25 - 1.5 hours after the start of pulping and were of the following composition:
Example Run No. Total solids Lignin Alkali % W/V % W/V % W/V ~
, ' 8 261 24.0% 5.67% 1.09%
9 310 26.9% 5.48% 3.04%
284 23.2% 4.17%
Il 286 23.2% 4.17% 2.28%

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1040Z~6 The oxidation charge was, as before, 1500 ml and the catalyst was either cupric sulfate pentahydrate in the amount of 3.65g or ammoniated manganese sulfate in the amount of 0.6g. The conditions in the reactor were:

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The invention permit~ the production of valuable chemical compounds, notably syringealdehyde and vanillin from kraft and similar wa~te liquor, thus providing a new practically limitle~s ~ource for these chemical~, the de-mand for which $~ now growing and the u~e of which as chemi-cal intermediates becomes ever greater.

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Claims (15)

What we claim is:

1. A process for the production of syringealdehyde from a lignin containing waste liquor of a hardwood alkaline or neutral sulfite pulping operation comprising: forming a charge of said waste liquor and alkali, passing oxygen contain-ing gas in intimate contact with said charge in a reactor to oxidize said liquor, neutralizing said oxidized liquor, extracting said neutralized oxidized liquor with an organic solvent thereby to separate an organic solvent soluble fraction containing lignin derived aldehydes and an aqueous fraction containing residual lignin and inorganic chemicals, treating said organic solvent soluble fraction with an aqueous solution of sodium bisulfite to form from part of said organic solvent soluble fraction an aqueous solution of a sodium bi-sulfite complex of syringealdehyde and vanillin, separating said aqueous solution of said complex from the remainder of said organic solvent soluble fraction, acidifying said aqueous solution to recover a mixture of syringealdehyde and vanillin, separating syringealdehyde from vanillin.

2. The process of Claim 1 wherein said lignin contained waste liquor is a Kraft black liquor.

3. The process of Claim 2 wherein said Kraft black liquor is a liquor withdrawn from a Kraft digester before termination of the cook.

4. The process of Claims 1, 2 or 3 wherein the charge contains about 0.5 - 3 parts of alkali to 1 part of lignin contained in said waste liquor.

5. The process of Claim 1 wherein the charge contains a catalyst consisting of a salt of a transition metal which is capable of existing in more than one oxidation state.

6. Theprocess of Claim 5 wherein the catalyst is one of the group consisting of salts of copper, manganese, nickel, iron and cobalt.

7. The process of Claims 1, 2 or 3 wherein the oxygen containing gas is passed in contact with said charge under a temperature above 100°C under pressure between 50 and 150 psig.

8. The process of Claims 1, 2 or 3 wherein the oxygen containing gas is air.

9. The process of Claims 1, 2 or 3 wherein the aqueous fraction containing residual lignin and inorganic chemicals is returned to the pulp mill recovery system for the recovery of heat and alkali values.

10. The process of Claim 1 wherein said separated aqueous solution of said complex is washed with an aliphatic alcohol having a chain of 4 - 6 carbons.

11. The process of Claims 1, 2 or 3 wherein the syringe-aldehyde is separated from vanillin by fractional distillation.

12. The process of making syringealdehyde from a lignin containing hardwood waste liquor of an alkaline or neutral sulfite pulping operation comprising forming a charge of said waste liquor and alkali, the proportion of alkali in said charge being between 0.5 and 3 parts by weight of alkali to one part of lignin contained in said waste liquor, passing air through said charge in a reactor at a temperature between 140° and 180°C under a pressure of about 50 - 150 psig to oxidize said liquor, neutralizing said oxidized liquor, extracting said neutralized oxidized liquor with an organic solvent thereby to separate an organic solvent solution fraction from an aqueous fraction containing residual lignin and inorganic chemicals, recycling said aqueous fraction to the black liquor recovery system of the pulping operation, concentrating said organic solvent soluble fraction, treating said concentrated organic solvent soluble fraction with an aqueous solution of sodium bisulfite to form an aqueous solution of a sodium bisulfite complex of syringealdehyde and vanillin, separating said aqueous solution of said com-plex, washing said aqueous solution of said complex with amyl alcohol, acidifying said washed solution to recover a mixture of syringealdehyde and vanillin, and separating syringealdehyde from vanillin by fractional distillation.

13. The process of Claim 11 wherein the waste liquor is a Kraft black liquor.

14. The process of Claim 12 wherein the Kraft black liquor has been removed from the digester prior to the termination of the cook.

15. The process of Claim 11 wherein the waste liquor is a spent liquor in a neutral sulfite semi-chemical operation.