AU4271872A - Extracting d-xylose and xylite - Google Patents

Description

Form

42,71 8 2 COMMONWEAITH OF AUSTRALIA

Patents Act, 1952-1969 -ENTY00LA ENyD L

CONVENTION APPLICATION FOR A PATENT

I/We LAEVOSAN-GESELLSCHAFT mbH Co.

of Estermannstrasse 17, Linz,.Austria,

HiRECDOLLARSlI |fitlrD0

hereby apply for the grant of a Patent for an invention

entitled: "METHOD OF EXTRACTING D-XYLOSE AND XYLITE"

which is described in the accompanying complete specifi-

cation. This application is a Convention application and

is based on the application(s) numbered: A4902/71 and A 806/72 for a'patent or similar protection made in Austria and in Austria,

on the 7th day of June, 1971 and on the 2nd day of Februa ry, 1972, respectively.

My/Our address for service is Messrs. Griffith, Hassel

Frazer, 67 York Street, Sydney, New South Wales, 2000,

Commonwealth of Australia.

2ED this 23rd day of May, 19 72. LAEVOSAN-GESELLSCHAFT mbH Co. KG By their Patent Attorney:

z38S of GRIFFITH, HASSEL FRAZER (Fellow, Institute of Patent Attorneys of Australia.)

To: The Commissioner of Patents, V Commonwealth of Australia. P A

P.46

RATION FORM FOR COMPANY APPLICATIONS, AUSTRALIA

Form 7,8. 9 /U

Regulations 12 and 12 (2) COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 69 DECLARATION IN SUPPORT OF AN APPLICATION FOR A PATENT

In support of the Application made by LAEVOSAN-GESELLSCHAFT mbH Co KG (Name of Applicant Company)

for a patent for an invention entitled: "METHOD OF EXTRACTING D-XYLOSE AND XYLITE"

I, RUDOLF WEIXLBAUMER of the Applicant's (Full Name of Individual Declarant) address, do solemnly and sincerely declare as follows:

f 1. I am authorized by the applicant for the patent to make this 'Declaration 'on its behalf.

2. GEROLD LORENZ

(Full Name of Inventor)

of Frieseneggerstrasse 35, Leonding, Austria, (Address)

is/are the actual inventor(s) of the invention and the applicant is the assignee of the said inventor(s).

3. The basic application(s) as defined by Section 141 of the Act, was/were made in AUSTRIA on the 7th day of June, 1971, (Country) and in AUSTRIA on the 2nd day of February, 1972 by LAEVOSAN-GESELLSCHAFT mbH Co KG. (Name of Applicant for Basic Application)

4. The basic application(s) referred to in paragraph 3 of this Declaration was/were first ap- plication(s) made in a Convention country in respect of the invention, the subject of the application.

Declared at WIEN, AUSTRIA tis (City and Country)

day of May, 1972

S(Signature)

To: ,,iV.OA, E, I.. The Commissioner of Patents, CANBERRA.

NOTE: Initial all Deletions and Alterations. No-witnessing and no legalisiaion.i" PATENT OF~LCt For a Non-Convention application delete paragraphs 3 and aadjniAttth.Altipn. For Multiple Pricrities incorporate details of all basic applications in paragraph 3. For application for a Patent of Addition add "of Addition" after the word 'patent" wherever the word occurs, and initial each such insertion. For Joint Application by a Company and an Individual amend form so that the individual declares he is one of the ap'licants and is authorised by the other applicant to make this declaration upon the latter's behalf (Paragraph and that the Company is an Assignee of a part interest in the invention from him (Paragraph 2.)

GRIFFITH, HASSEL FRAZER, Box 2133, G.P.O., SYDNEY 2001. AUSTRALIA.

Form COMMONWEALTH OF AUSTRALIA

PATENTS ACT 1952-69

COMPLETE SPECIFICATION (ORIGINAL)

F0~ 'OFFICE USE: Class -ftt~-G~ Application Number Lodged ~2t v

~r\JT. CJ~~JZ\3 C-C) C- Lk- II !i II R Complete Specification Lcdged: I Published: Ot-9 Priority A- TYL (3,-Ioq h' L Th 11 0A- 1 C)G Related Art

TO BE COMPLETED BY APPLICANT Name of Applicant: LAVOSAN-GESELJSCHAFT mbH Co. KG

Address of Applicant: Estermannstrasse 17, Lainz, Austria.

Actual Inventor, GEROL~D LORENZ

Griffith, Hassel Frazer, Address for Service: 67 York Street, SYDNEY N.S.W. 2000 AUSTRALIA.

Complete Specification for the invention entitled: "MVETHOD OF EXTRACTING D-XYLOSE AN'D XYIJITE"

Thr following statement is a full description of this invention, with the best method of it wntoX -s

o.3. 01

'I

The present invention concerns a new and profitable

method of extracting xylose and xylite from cheap and

easily-obtainable raw material.

On account of the increasing use of xylite in medical

therapy and dietetics, additional economical and efficient

methods of producing it have been sought and found. The

main raw materials for the production of the intermediate

product xylose, are agricultural by-products such as maize

cores, oat husks, cottonseed husks, rice husks, sugar cane

residue (once the juice has been extracted) (bagasse),

straw, and the like. Whilst the cost of such materials

is relatively low, their collection and storage until they

are processed can, however, be expensive. There is also

the problem of the disposal of the remainder, the utilis-

ation of the residue, or the sale or destruction of the

remaining waste.

A further source material for the production of

xylose is the sulphite liquor of deciduous trees, which

is produced in great quantities, but is mostly only

reduced and burnt for the recovery of the used chemicals

contained, and to lessen the amount of waste water.

This solution contains circa l4%xylose, in addition to

about 14% of other substances, above all oligomerous

xylose as well as Lignin sulpho acids and inorganic salts.

This high degree of impurities has hitherto made the

recovery of xylose from sulphite liquor very wasteful and

technically very time-consuming. Freudenberg Chem. 28 Ber. 80 (1947) 53. Sydkemi Malmo Austrian Patent Nr.289,845,

Sydkemi Malmo, German Offenlegungsschrift Nr. 1 939 695,

A/S Norcem, Oslo, German Offenlegungsschrift Nr. 1 929 268).

These methods are always based on extractions in

which the xylose can be separated from the impurities

because of its easier solubility in non-polar solvents

such as water. For that purpose, however, the acid

bisulphite solution must always be treated by steam to

increase its concentration. This concentrating process

must proceed carefully, in order to avoid break-down..,

This careful procedure can be attained either by neutralising

the acids with appropriate alkalis before the steaming

process, or by using steam at a temperature not higher

than 700 centigrade, or, better still, by using both

measures together. Owing to the steam treatment of the

initial solution, both processes are already expensive,

for not only can the chemicals not be completely recovered,

but also the energy yield at a lower temperature of steaming

is significantly smaller. It would therefore, be

advantageous to be able to extract xylose from the

initial sulphite liquor in order to be able to concentrate

the rest of the sulphite liquor for agricultural purposes.

A relatively simple method of separating the high-

molecular components (molecular weight over 2000) from

a sulphite liquor solution would be through the use of

dialytic membranes. In this way, the low molecular

part of the solution passes through the pores of a

cellulose membrane, whilst the high molecular part scannot

28 penetrate this: for example, 82% of the contained sugar would be dialysed in one hour through a 0,4 35m 2 dialytic membrane out of 76 ml of the sulphite liquor solution, whilst 82% of the Lignin components would be held back.

Peniston J. Am. Chem. Soc. 70, (1948) 1324-28).

Through the utilisation of a fine-pored membrane, one

could lower still further the limits of the molecular

weight of the amalgamations which are able to be dialysed;

at the same time, however, with this, the speed of

dialysis would be reduced still further. Thus, for ,IO 6 r technical application this method of dialysis seems to

be imprac'icable.

It has now been found that one can carry out the

separation of the high-molecular components from the

low-molecular components of the sulphite liquor solution

relatively quickly and inexpensively if one leaves the

I- low-molecular portions of the sulphite liquor solution

to diffuse in a gel with as highly defined a pore-diameter

as possible, and if the sulphite liquor solution is kept

away out of the gel and the portions which have been i; t diffused therein are washed out with water again. All

hydrophilic gels with clearly defined pore-measures are

considered as gels in this context. Amongst the cheapest

are gels of a synthetic resin interchangeab.l ion base,

but gels on a base of saturated polysaccharides, as for

example, saturated Dextrane, sulphonated charcoal and

others can also be used. In gels in ion-exchange-active I.

groups that dissociate in the sulphite liquor solution

used, a further effect adds itself to the molecular

li- I; i I sifting action, and indeed ions from the gel structure are also excluded by the Donnan-Membrane, which are included as ions of opposite charge in the ion-exchange- matrix. In this way, not only the high-molecular con- stituents but in practice also, all the ionised components of the sulphite liquor solution are separated from the undissociated low-molecular portions. The addition of both effects makes the use of gels with ion-exchange-groups eminently suitable for the separation of Xylose from sulphite liquor.

SThe separation of Xylose from sodium chloride with

the help of ion-exchange, through ionic exclusion that

depends on the effect of the Donnan-Membrane, is known

in the literature (D.R.Asher, Ind. Engng. Chem. (1956)

(1465-66). Now one cannot conclude simply on the possib-

ility of separation of the sulphite liquor solution from

this description of such a separation. In this process

there are namely only circa 25% of non-saccharine matter

inorganic salts, such as Calcium Magnesium- and

Potassium bisulphite, whilst circa 66% of lignin fragments

are there, which to some extent are also not sulfonated,

and therefore cannot be separated through ionic exclusion.

A further advantage of the new method becomes evident

in th4 separation of the Xylose from oligomerous saccharides

of the sulphite liquor solution. In an incomplete hydrolysis

of water-insoluble polysaccharides oligomerous fragments

also go into solution. There o.ligomerous substances

28 are a strorghindrance to crystallisation, one effect, that is used for example in the starch hydrolysis to glucose syrup, is used to prevent the glucose from cryst- allizing. Such hindrances to crystallisation are not desired at all in the extraction of Xylose, since they can strongly diminish the gain of crystalline Xylose.

The execution of the procedure can now take place in

different ways;

The simplest is that which is analogous to a

chromatographic separation in which a gel is used

in a chromatographic column. A suitable quantity of

the Xylose solution is placed in this column and at the

same time the water surrounding the gel substances is

drained off. The applied quantity of the Xylose solution

must stand in appropriate relation to the volume of the

column, so that on the one hand, a sufficient separation

of the Xylose from the impurities is guaranteed and on

the other hand, that too strong a dilution of the solutions

is avoided. After the application, it must again be rinsed

out with water, so that the mixing region remains as small as possible. At the other end of the column, samples will

be gathered, tested for the Xylose content and the solutions

containing xylose will be reduced to a syrup. Out of this

syrup, after inoculation, the ,xylose will eventually be

crystallised with the addition of an organic solvent, or introduced directly into a catalytic hydrogenation step.

The disadvantage of this method is that in all cases

the solutions coming out of the column are more diluted

28 than those put in, and that for the extraction of the separable spent liquor as also for that of the Xylose, great amounts of water have to be evaporated, and for that purpose valuable energy has to be expended.

It has now been found that one can avoid the strongest

dilutions if one makes use of either the principle of

counter current flow or that of open concentrations of

diluted solutions in the use of the method. The

principle of open concentration has already been described

in the method of exclusion of ions and is employed in

the reduction of ethylene glycol in the separation of

sodium chloride and ethylene glycol Simpson and

W.C. Baumann, Ind. Engng. Chem. 46, (1954) 1958-62).

In more recent times this method has also been described

in the purification of saccharose from molasses (D.

Gross, Int. Sugar J. 1971, 298-301 and 330-334). The

fact that one can utilise this principle also for the

separation of Xylose out of solutions heavily laden with

impurities is new and the results could not be foreseen.

The application takes place in the following manner:

The gel substances are treated through transfusion with

running, fresh impure Xylose solution (for example

sulphite spent liquor) until the concentration of

Xylose in the Gel is in equilibrium with the xylose

concentration of the fresh solution. In this case the

gel substances can move around by themselves (counter-

current action) but can also be filled in the columns,

wherein running, fresh solution is introduced. In this 28 connection the Xylose is again dissolved out of the

Gel, while the gel substances in the counter current

to the water that is concentrated up to a maximum,

are led and thereby give up the entire Xylose content,

or while, with the solutions of falling Xylose con-

centration from the preceding cycle succesively, and at

last the bed of gel becomes washed out with water.

Through the setting up of several pillars, and the use

of a pillar with the discharge solution of a preceding

one, a semi-continuous process can be originated. In

an operation it is always the Xylose which is reduced

in strength, or the Xylose- free initial soluticn, and

the concentrate richest in Xylose which is distilled,

and a corresponding quantity of the initial solution

is newly applied. In a set-up lye, with circa 4l/

Xylose and circa 14o non sugar substances, the extracted

spent lye contains circa 10-11% solid matter, the

extracted Xylose solution 8 10%, so the concentration

of Xylose is essentially higher than in the solution

of spent lye. The preserved straw-coloured Xylose sol-

ution will hereupon eventually be evaporated under

insertion of a conventional ion-exchange-cleansing

action, and the Xylose will be crystallised out of the

concentrate by the addition of an alcohol, or again

directly hydrogenated.

In the technical execution of the chromLatographic

method it is exceedingly difficult to keep the column

structure entirely homogeneous. Therefore it can 28 be almost unavoidable, especially in the larger

-L- density differences of the individual zones, that these became crooked, oblique, or produce tails or tongues. This phenomenon leads to the fact that the distillations distribute themselves over a larger volume, the concentrations lie lower and the mixing z,nes grow larger. In longer columns, one seeks to suppress this phenomenon by radial mixing.

An improvement in the method of concentrating

diluted solutions in columns has been found with

the following principle: The saturation of the gel

with Xylose is passed through the original solution

from below until at the upper end of the column the

almost unaltered original material comes out. Thus,

by this means, the mixing zone is lessened by the

outgoing lignin distillations and this is at the same

time kept in a high conc4ntration. Joining with the

diluted Xylose solution or water, the Xylose will again

be rinsed out from above. Through the now ever present

increase in density from above to below, no convection 2on the ground of difference in density can enter, even

when the apparatus is stopped, and thus an unwanted

mixture in the disturbances has been excluded.

The following examples show the possibilities for the

application of the processes, even though they are

not limited to these:

Example 1. 2 In a tube with an inner cross-sectional area of 5,3cm 28 320 ml of stepped cross-linked Dextrane of the Type

Sephadex (R)G 1C are filled up and in a temperature of

degrees, 15 ml of beechwood sulphite liquor is added

and then washed with water. With a velocity of flow

of 2 ml/Min., the following distillations were collected,

whose solid matter content was determined by the measure-

ment of the 0 Brix on the refractometer; The Xylose content

was established by thin chromatographic film (layer, emulsion).

(Silicic gel, middle fraction: Ethenyl nitril: carbon

disulphide; Water 85:5:10, three times run through, spray

medium; Diphenylamin aniline phosphoric acid, quantity

of coating each time one ul).

Distillation Volume °Brix number milliliter

1 112 0

2 3,0 2,2

3 5,0 4i,8

4 3,7 5,1

3,9 5,2

6 4,4 5,4 dark coloured

7 4 4,4

8 3,8 4t4

9 4,0 4,0 3,2

11 4,1 2,1 light brown

12 4,2 2,6 yellowish

13 4,1 2,4

14 4,0 2,0 Traces of Xylose 28 15 4,2

Distillation Volume °Brix number milliliter

16 4,1 2,31 little Xylose 4,3 2,6 17

18 4,1

19 4,0

4,0 3,4

21 3,8 3,4

22 4,0 3,9 a -lot of Xylose 23 4,1 3,9 almost colourless 24 3,9 4,1

o 't *r 25 3,9 3,2 *o 4f

0 t 26 3,9 2,6

27 4,0 1,8 little Xylose Oft

o 0 28 4,0 1,2 traces of (±00 Xylose ft±ff 29 4,0 0,9

4,0 0,8

31 3,9

32 4,1 0,3

Example 2

Into the tube of the previous experiment are put 31 5 ml

of weak acid ion interchanges in the H-form (Imac Z

dry ground and sifted particle size 0,15 to 0,30 mm)

and in a temperature of 60 degrees, 15 ml of beech wood

sulphite liquor (pH value circa 1,7) applied and finally

washed through with water at a velocity of circa

Min. The following distillations were collected and were

examined as in the previous experiment:

Volume in 0 Brix Dis-cillation number milliliters 1 118 0 2 5,8 0,4- 3 6,4 1,3' 4 6,6 394 dark coloured

6,6 4,6 6 6,4 3,4 7 6;5 2,3 86,0, 2,0 brown

9 697 2P5 yellowish brown 410 6,5 2,8 yellow

U:11 6,6 2,9- traces or Xylos e F .,12 7,1 13 6,7 3,6 14 6,5 3,6 a lot of 6s 3$2Xylo se

16 5,5 2,7 yellow sh

17 6s5 9 186,7 1s4 traces of 19 6,6 0,7 Xls

6,7 003 Example 3 In the glass tube of' the preceding experiments are put 280 ml with sulpho-propyl groups of' modified flextrane gel SP Sephadex G 25 in the H+ -Form, in a temperature of' degrees, 1'5 ml of' beech wood sulphite liquor is added and washed through with water at a velocity or 2 times 28 3ml/lMin. The following distillations were collected:

Di sti llat ion Volume in 0 rix ~number milliliters

1 57 0

2 16,0

3 14,2 4t4 4 13,0 4,9 dark coloured. 12s5

6 12,3 1 ,6

11,5 1 ,2

11 ,0 1,0 b.-own

9 1,3 yellow 1 ,4 yellowish

11 !s,2

12 1,3

13 7,3 0,9

'4 7,0 0,7 traces of Xylose 7,0 littel Xylose 17 7,0 018 almost colourless 791 1 92

19 7s4 203

703 2,6 a lot of Sylose 21 22 23 24 9,6 0,7 little Xylo se 903 091

Example 4 In a glass tube with an inner diameter of 27,5 mm is

placed 1 1 of strong acid ion interchanges on a Polystyrol

base with a Divinylbenzol content of 4% and particle size

of 0,15 to 0,30 mm in the H+-Form, to a high of 1700 mm,

and the entire column is warmed to 60 degrees by a

heating tape (band). With a pump 72 ml of original

liquor from a magnesium sulphite cooking of beechwood

are now added within 10 minutes, and finally rinsed

through again with water at the same velocity. The liquid

which was discharged was collected in the following

distillations

Distillation Quantity Refractive 20 Brix Colour index nD 1 331,7 1,3330 0,0 clear as water 2 50,0 1,3395 4,5 dark

3 77,0 1,3445 7,7 dark

4 20,1 1,3400 4,8 brown

20,0 1,3385 3,6 light brown 6 20,9 1,3346 1,1 yellowish

7 17,2 1,3346 1,1 yellowish

8 21,9 1,3342 0,8 slightly yellowish 9 21,0 1,3355 1,7 almost colourles s 20,6 1,3388 3,9 almost colourles s 11 22,0 1,3406 5,3 almost colourles s 12 18,0 1,3406 5,3 almost colourles s 13 17,2 1,3372 2,9 almost colourles s 14 17,4 1,3348 1,2 almost colourles s 77,5 1,3332 0,2 almost colourles is 16 34,8 1,3331 0,1 almost colourlesis

On the thin layer chromatogram it could be established

that nearly the whole Xylose in distillations 9 to 14

was present.

Example

100 grams of washed and dried hemicellulose from a

neutral sulphite cooking were heated with 000 ml of

water with theaddition of 5 grams of concentrated sulphuric

acid for 64 hours until boiling to refluy, it is then strained and squeezed out and the residue washed again

in boiling water. The combined filtrates were then steamed

in a bath temperature of maximum 40 degrees C in a

rotation vaporiser to 150 ml, wiltered with the help of

siliceous earth, and the filtrate added to the column of

Example 4 at a speed of 7,2 ml per minute, and rinsed

again with water at the same speed. The collected

distillations were:

Distillation Quantity in Refractive index 0 Brix milliliters

1 345,0 1,3330 0,0 2 22,6 1,3400 4,8

3 23,4 1,3446 7,8 4 23,2 1,3448 7,9 23,3 I,3448 7,9 6 21,9 1,3445 7,7 7 21,9 1,3444 7,6 8 22,5 1,3402 5,1 9 22,7 1,3446 7,8 28 10 22,0 1,3425 6,6

Disillation Quantity in Refractive index Brix milliliters

11 22,6 1,3420 6,2

12 24,9 1,3486 10,6

13 22,8 1,3539 13,7

14 25,4 1,3532 13,5

23,4 1,3491 10,8

16 26,5 1,3402

17 23,4 1,3361 2,2

18 26,5 1,3349 1,3

19 22,2 1,3345 0,4

Fractions 11 to 18 were combined and over 100 ml of cation

exchange Duolite C 25 in the H+-Form and 100 ml of Anion

exchange Duolite A 6 in the OH- Form were filtered

and washed through with 200 ml of salt free water. The

clear-as-water filtrate was steamed to 10 ml with a

spatula spoon of Raney-Nickel in an autoclave under e

pressure of 100 Atm in a temperature rising from 80 to

130 and hydrogenated for 24 hours. It was filtered by

a catalyst, steamed to a thick syrup (13,2 g) dissolved

in 13,2 g of ethanol and inoculated with xylite. After

agitation, it was then left to cool down in the refrigerato

ory, filtered with suction after 18 hours, washed with

ml of cold ethanol and dried. The yields were 9o3 grams

of white Xylite with a specific (special) rotation (a)

29 0,190 and a melting point of 89 to 910C.

Example 6

To the ion exchange column of Example 4,1000 ml of beech

28 sulphite original liquor Lsre added in 7 parts, 143 ml within 20 minutes, from time to time, ard finally rinsed through with 380 ml of water within 50 minutes. Then the impurities of the subsequent applications came out at the lower end when the Xyl6se content of the preceding came to the end. For example, the following distillations were obtained for one cycle: 0 Brix Distillation Quantity

1 22,0 9,4

2 22,8 8,2

3 23,5 6,1 impurities of the b 0 a 0 0U 24, 65 preceding applications 4 24', 4+ 6, a0

21,4 4,9 0

6 19,7 6,4 S*

7 22,4

8 21,1 7,8 Xylose distillations of the preceding 9 21,4 7,3 applications za 10 20,4

11 20,9 3,2

12 21,4 2,1

13 21:,:5 1,1

14 22,6 2,8

228,0 899

16 20,4 6,2 impurities

17 25,0 .6,8

18 20,0 5,7

19 21,7 6,4

21,7 7,6

21 21,6 7,8

Distillation Quantity °Brix

22 21,8 7,6 Xylose distill- ations 23 18,8 6,2

24 18,0 39

20,2 1,8

26 14,1 6,1 Impurities of the subsequent applic- ations

The Xylose distillations of all seven lots are combined,

heated by steam to 500ml, and over 100 ml strong acid

ion-exchange resin (Duolite C 25) in the H+-Form and over

350 ml weak basic ion-exchange resin (Duolite A) in the

OH- Form filtered, and washed through with 500 ml

Water. The colourless Xylose- bearing filtrate is heated

by steam in a rotation evaporator to a thick syrup, 66

grams, brought to dissociation with 120 ml of ethanol,

inoculated, and after standing for a few hours at room

temperature is left to stand overnight in the refrigerator.

The precipitated crystals are filtered and compressed

i (squeezed) and washed through with 50 ml of cold ethanol.

After drying in a vacuum drying chamber 38,5 g of white 20 Xylose are obtained with a specific rotation D of

+19,48°. The thin layer chromatogram showed a very trif-

ling impurity of glucose. So that permits a yield of 98% Xylose to be reckoned.

Example 7

150 ml of strong acid ion-exchange on a Polystyrol base

with circa 4% Divinylbenzol (Dowex 50WX 4) and a particle

28 diameter (grain diameter) of 0,15 to 0,30 mm is put with water into a glass tube with an inner diameter of 27,5 mm, the overlying water is drained off and 10 ml of beech wood sulphite liquor is added. The liquid is drained off from the bottom of the column with a velocity of 1 ml/min. and collected in distillations. As soon as the sulphite liquor has completely penetrated the ion- exchange-plane, carefully rinse through with water to obtain the smallest possible mixing zone. The thin layer chromatogram showed that the Xylose was contained in the distillations 12 to 18, while the strongly coloured impurities were found in distillations 2 to 8.

Distillation Quantity in °Brix milligrams 1 52,8 0,0

2 9,6 3,8

3 7,4 7,2

4 2,9 6,4

3,0 5,6 6 4 4,9

7 1,6 4,2

8 3,2

9 3,0 2,2

3,0 1,4

11 2,9

12 2,8 1,4

13 4,0 2,9

14 5,0 4,3

4,9 4,9 28 16 4,8 3,4

Distillation Quantity in 0 Brix milligrams

17 4,4 1,6 18 2,0 0,9 19 8,2 0,4

Example 8 170nl strong basic ion-exchange with a Divinylbenzol

content of 8',0 (Dowex 1 x 8) and a particle diameter

of 0,15 to 0,30 mm were brought with a solution of grams of sodium bisulphite in 200 ml of water to bisul-

phite form and bathed with 500 ml. To this column was

added 10 ml of beech wood sulphite liquor and after

penetration in the ion-exchange bed was washed through

with water. From the end of the column the following

distillations were collected with a velocity of

about 1 ml/min.

Distillation Quantity °Brix

1 40,0 0,0

2 9,5 1,1

3 5,6 6,2 4 6,7 6,4

4,8 3,9

6 5,0 1,9

7 5,7 0,7 8 4,6

9 4,8 0,9

4,8 0,6 11 4,8 0,2

28 12 4,0 0,2

BfSilCl: y i h^ u i

There was no Xylose in the distillations 1 to 6,

the majority was in distillations 7 to 10, yet the following

distillations all still contained traces of Xylose.

This delayed emergence of the Xylose from the column can

be traced to the development of a Xylose Bisulphite

combination (amalgamation).

Example 9

175 ml of ion-exchange on the base of sulphonated coal

(oarbon, charcoal) (Imacti Dusarit S) with a grain size

smaller than 0,15 ml under dry conditions, in a dry

state, were separated from the finest suspended particles

were brought with 20 ml of concentrated sulphuric acid

in 800 ml of water in the H Form, and washed with water;

until the water that ran away showed a pH-value of 5. In

a glass tube with an inner diameter of 27 mm the water

was decanted, 10 ml of beech wood sulphite liquor was

added, and rinsed through with water with a velocity of

1 ml/min. 0 Brix Distillation Quantity

1 64,2 0,0

2 3,0 0,9

3 3,0 2,9,

4 2,7 3,3

2,9 4,2 no Xylose

6 2,8 3,6

7 2,7 3,6

8 2,7 2,9 28 2,2 9 7,6

-21.

F I -Th

Distillation Quantity °Brix I 7,3 1,4

8,9 1,3

4,2 1,3 traces

1,3 of

2,9 1,6 Xylose

2,9 1,9 2,9 2,1

2,9 2,0 Xylose

18 3,0

19 2,9 2,9 1,4 21 2,9 0,9 The greatest quantity of Xylose was found in the distillat:Lons 13 to Example Desiccated weak acid ion-exchange resin on the base of poly acrylic qcid (Imacti Z 5) was ground in a grain diameter finer than 0,15 ml, allowed to saok in water to a volume of 400ml, and through mixing up by stirring with a suspension of 36 mg of magnesium oxide in 200 ml of water with the addition of 24 g of acetic acid was transformed into the magnesium salts form. Of this resin,

180 ml was put into a column with a diameter of 27 mm and to it was added 10 ml of a beech wood sulphite liquor, that was neutralised by a magnesium oxide with a pH-value of 7,2. With a speed (velocity) of 0,8 ml/min, the following distillations were collected.

Distillation Quantity Brix 0 I3rix Distillation ~uaxitity 68,5 0,0 11,2 310 11 ,8 11,6

5,9 7,7 3,2 5,4 little Xylose 3,4 38 8,2 8 4,2 7,6 Xylose 9 4,4 498 4,3 2,1) 11 4,0 0,6 little Xylos e Example 1i 400 ml of a strong acid Cation exchange in the H+-Fom after removal of the externally accompanying water, were agitated with 150 ml of beech wood sulphite spent liquor for ten minutes and finally separated again by centrifuge. The centrifugally separated solution was agitated with a new exchange, and the centriguged exchange was agitated with a new sulphite waste liquor and then again separated. After execution of a number of steps of a kind of diffusion diagram, the sulphite spent liquor contains only a fraction of the original Xylose, and can

be thrown out; at the same time, the exchange is saiturated with Xylose. This saturated exchange is now agitated with 200 ml of water and the exchange recondit- ioned with xylose solutions or water following the same schedule. The extracted exchange will finally be used

-23" again for the saturation with beech wood waste liquor.

The diagram is presented in figure 1.

In 200 ml of inserted beech wood original liquor with

of solid matter, 250 ml of xylose- free spent liquor

contain 10 to 11o of solid matter, and the 150 ml of

&ylose solution, 9 to 10% solid matter of which they are

about 6 to 7% Xylose.

Example 12:

In an apparatus in which the ion-exchange-grains can be

accelerated in the counter-current to sulphite spent

liquor from deciduous trees, strong acid ion-exchange in

the H -Form is introduced by a shank (p'llar). This

exchange sinks into that part of the apparatus in the

same extent that the lowest part of the apparatus is

accelerated upwards with the help of an endless screw.

In the counter-current sulphite spent liquor from decidu-

ous.-trees is conveyed, that is extracted through the

exchange Xylose, The exchange, which is saturated with

Xylose is released from the accompanying sulphite

waste liquor through the spraying with a little xylose

solution, and is treated in a similar apparatus in the

unter current with water, in order to wash it again to

be xylose free. Figure 2 will make clear and illustrate

the diagram.

As an example for a run through the following figures

are valid:

Runthrough of original liquor 4,000 ml 18% solid matter 28 Runthrough of water 3,000 ml

Discharge of spent liquor 5,200 ml 9% solid matter

Discharge of Xylose solution 2,800 ml 10/o solid matter

The duration of the liquids is governed by the run

through speed of the exchange through the speed of rotation

of the endless screw.

Example 1j In a column with an inner diameter of 27mm a strong acid

Cation-exchange in the H -Form with a particles size of

0,15 to 0,30 diameter, is filled to a height of 1,800-

mm, and to it are added in sequence with a speed (velocity)

of 7 ml per minute:

Distillations 112 ml from the previous experiment Original liquor 280 ml with circa 4% Xylose,

1 other sugars and

14o lignin and inorganic salts,

Distillations 33-42 and 57-80 640 ml from the previous

experiment, Water

After first rurnings of 378 ml of water, the following

distillations of each 14 ml were collected and tested on

the refractometer for their solid matter content:

Distillation oBrix Distillation 0 Brix

1 1,5 41 15,0 2 4,0 42 14,8 brown

3 6,2 43 14,5

4 8,0 44 14,4

8,8 45 14,2

6 9,5 46 14,1 28 7 10,0 47 13,9 yellowish brown

Distillation istilatio Brix Distillation 0Brix rx

10,1 48 13s7 9 10,5 49 13,2 10,6 50 13,0 ii1029 51 1299 12 11,4 52 12s7 13 12t5 53 12S2 14 1301 54 1290 yellow 13,5 55 11,5 16 14,1 5r,6 1192 17 14t4 57 10,5 1814,6 58 10,,2 19 1520 59 9,6 15,3 dark 60 9"1 21 15,t5 61 9 22 1 5,8 628-2 23 16,2 63 24 16s4 64 722 16,6 6568 26 16,9 66 6,4 27 17s7 67 6 s2<iight yellow -straw col- 2818s4 68 5,6 oured 29 18s 69 1912 70 503 31 19,6 71 521 32 19,6 72 4,6 33 18, 73 283.4 17j6 7432

-26.,

Distillation OBrix Distillation 0Brix

16,4 75 3,3 36 16,2 76 2,7 37 15,9\ 77 2,4 38 15,6 78 1,9 39 15,4 79 1,4 15,2_brown O From distillation 23 there are increasing quantities of Xylose to be found on the thin layer chromatogram. Distillations 1 to 24 appear as xylose-free waste liquors, distillations 43 to 56 as crystallised Xylose solutions, the remaining distillations will be inserted in the next work cycle analogous to these. Distillations 1 to 24 contains 7,8F solid matter, distillations 43 to 56 contain

9,8fo. Example 14 Four columns with an inner diameter of 152 mm are filled to a height of 1,100 mm with a strong acid Cation-exchange in the H -Form and with a particle size of from 0,15 to 0,30 mm. To this column 20 litres of beech wood sulphite waste liquor are added and finally washed through with water. As soon as the solution drains off dark below, it is collected and the first 7 litres are rejected as waste liquor. The following discharge is immediately added to the 2nd column, until the concentration of solid matter is removed. At this moment it is interrupted, 6,0 litres of the original liquor is added to column 2, and finally 28 it is re-washed with the discharge liquor from column 1.

Likewise the first 7,0 litres of the dark discharge

liquor from column 2 are thrown out and again 6 litres

of fresh original liquor added to column 3. After

passing through the fourth column the last runnings

have become so concentrated that a part of them (2 litres)

can be drawn off as light coloured Xylose solution with

a solid substance content of 9o. The discharge liquor

from column 4 is now again added as before to columna 1

and in each of the subsequent columns the first 7 litres

as waste liquor and in turn circa 3 litres each drawn off

after solid matter content and intensity of the colouring

(as amount for the content of inorganic salts and lignin

constituents). As example for the extracted material from

a column, the following values were given. (The extinction i

is measured against a glass standard.) i

F Running off, discharge, drain °Brix E I 0 0,1 0,03

1 9,5 1,35 i. 2 12,2 1,45 3 13,1 1,45

4 13,9 1,45 14,9 1,45 6 15,7 1,45 7 16,6 1,45 8 17,1 1,45 9 18,0 1,45

19,0 1,45

i -1

Running off~discharges 0 Brix E drain

11 20,93 1,45 12 21,1 1,45 13 21,95 1,45 14 21,9 1,45 22,0 1,945 16 22,6 1,45 17 23,2 1,45 1824,6 1,45 19 24s9 1,45 23,7 1,40 21 22s5 1,20 22 20,9 1,00 23 18,,4 0,92 24 16,8 0,73 16s4 o,64 26 1503 0,51 27 14,5 0,4+6 2813,0 0,28 29 11,5 o,16 9,9 0,14 31 9,0 0,10 32 732 0,085 33 4j8 34 2,9 0,055 1,9 0,050 36 Og9 0,0,+o

Example

In this example the difference in increase of the concentration

of solid substances in the waste liquor after the columns

is to be shown, once when the beech wood sulphite waste

liquor is added from below, and the other time when it is

added from above. A column with an inner diameter of 5,3 2 cm was used, 320 ml of weak acid of exchange resin Imac

Z 5 in the H-Form were put in and treated at 600. The

exchange bed was loaded with beech wood sulphite waste

liquor with a velocity of 5 ml/min, and the solid matter

content was established for each minute of the light

measurability in oBrix on the refractometer.

Time from the Total quantity Application Application beginning of the up to the moment from below from above application of measuring 0 Min. ml Brix Brix

17 85 0 0 18 90 0 2,3

19 95 0 3,3

100 0 4,3

S21 105 0

22 110 2,4 5,9

23 115 5,1 6,9

24 120 7,5 7,4

125 8,2 i,0

26 130 9,5 27 135 10,2 10,1

28 40 10,8 10,7

28 The further increase proceeds in practially identical manner.

I _i_

Claims (1)

1. The claims defining the invention are as follows:

   1* Method for the extraction of Xylose and Xylite

   wherein there is brought into contact a gel having

   clearly defined pore diameteis with a vegetable hydrolysate

   containing xylose, whereby the gel is saturated with

   xylose, the impure solution is removed and the Xylose

   washed out of th4 gel with water or aqueous xylose solution;

   whereupon the xylose solution is concentrated and thence

   either the xylose is crystallised or this concentrate is

   hydrogenated tnd thence is crystallised Xylite.

   2. Method according to Claim 1 wherein there is

   employed as xylose-containing vegetable hydrolysate the

   waste liquor from an acid sulphite treatment for the

   preparation of cellulose from deciduous trees.

   3. Method according to Claim 1 or claim 2, wherein there

   is employed an ion exchange as a gel.

   4. Method according to any one of claims 1 to 3, wherein

   one adds an organic solvent for the crystallisation of

   Xylose or Xylite.

   Method according to Claim 4, wherein one uses Methanol

   or Ethanol as organic solvent.

   6. Method according to any one of the previous Claims,

   wherein the method of alternating addition of Xylose

   solution and water to the columns containing gel is

   conducted semi-continuously.

   7. Method according to any one of the previous claims,

   wherein the gel bed, in order to avoid waste formation is

   occasionally rinsed back, anid thereby undergoes treatment

   -31- .j l t with acids and lyes, in order to remove adsorbed molecules from the gel.

   8. Method according to any one of the previous Claims,

   wherein the process is carried out at temperatures between

   and

   9. Method according to any one of the previous claims,

   wherein the gel substances, preferably in counter-current

   to the impure Xylose solution, are saturated with xylose,

   and finally the xylose with water or diluted clean

   Xylose solution in counter current is extracted therefrom.

   Method according to claim 9, which is carried out

   continuously.

   11. Method according to any one of the previous claims,

   wherein the impure Xylose solution is conducted over the

   columns of gel substances, which are connected in

   series whereby the extracted material of the preceding

   column can at once be added to the next column and only

   xylose-free discharge and at tires the most concentrated,

   clean xylose solution is drawn off from the circuit or

   cycle.

   12. Method according to Claim 11, wherein one adds to

   the existing gel in the column the impure xylose solution

   from the lower end of the c-olumn, until the practically

   unchanged solution emerges from the upper end and upon

   this washes out again from above the xylose with diluted xylose solution or water.

   Dated this day of 7 r

   LAEVOSAN-GESELLSCHAFT mbH Go. KG By their Patint Attorney:

   -32- or GU J.LT HASSEL FAZER