Svnthesis of Tartaric Acid

BY THE HYDROXYLATION OF MALEIC ACID

JAMES RI. CHURCH AND RUTH BLUiMBERGi

Columbia University, New York, N. Y .

Tartaric acid is available commercially only as a by- reaction occurred when a 30YG aqueous solution of maleic
product of the wine industry, with large quantities of the acid was heated with a 35YG hydrogen peroxide solution
acid and its salts being consumed in the production of i n the presence of 0.5% of tungstic acid as the catalyst.
foods and drugs. This investigation was undertaken to Using a molar ratio of 1.5 to 1 of the reactants a t a tem-
devise a suitable method for the synthesis of tartaric acid, perature of 80' to 100" C., a high yield of the pure racemic
utilizing fairly inexpensive chemicals and relatively simple tartaric acid, representing over 9594 of the theory of
operations, and thus providing an economical and feasible maleic consumed, or 8401, of the theory of peroxide, ')cas
commercial process for this important chemical inde- obtained.
pendent of natural source and consequent price fluctua- This method of synthesis offers good possibilities for a
tions. commercial process in view of availability and low cost of
Maleic acid was chosen as the starting material, in view starting materials, simplicity of operations, utilization of
of its structural relation to tartaric acid and its availability standard inexpensive equipment, practically quantitative
from existing maleic anhydride processes. Among the yields with no by-product formation, and a high quality
oxidizing agents investigated for a combined oxidation product requiring little or no purification. Based upon
and hydrolysis required for the hydroxylation, hydrogen these results, a practical process for the synthesis of tar-
peroxide was found to be the best. The most favorable taric acid from maleic acid is suggested.

T ARTARIC acid is obtained from the lees and argols, by-

products of the wine industry ( 4 , 5 , 1 1 , 5 3 ) ;although many
syntheses of tartaric acid and its salts have been suggested, none
tions-namely, d-tartaric and 1-tartaric which exhibit optical
activity, and racemic dl-tartaric and meso-tartaric which are
optically inactive (14, 19). The configurations of these tartaric
thus far have been used industrially, mainly because low yields of acids are shown in Table I with some of their significant propnr-
acid from these methods and high costs of starting materials ties.
make them uneconomical for commercial utilization.
Within the past ten years the price of tartaric acid and its salts
has varied as much as 50%, as might be expected when the source
of the raw material is a by-product of another industry. The TABLE
I. TARTARIC
ACIDS
success of our expanding organic chemical industry has been d 1 Meso Raoemic
based on continued development of synthetic processes to re- COOH COOH COOII COOH
I 1
place the natural products, and i t would seem probable that an HbOH HOCH HOCH AH(OH)
Structure I
economical process for the synthesis of tartaric acid would take HOJH HbOH HOCH dH(0H)
its place with other synthetic processes of the industry for the bOOH bOOH b O O H dOOH.HaO
production of tartaric acid in the future. With the price stabi- M.p., 0 c. 168-70 16840 159-60 205-6
lized and the purity of the synthetic product guaranteed, new Sp gr 20 C 1.760 1.760 1.737 1.697
soi., g:)ioo mi./zoo c. 139 139 125 20.6
uses for tartaric acid and tartrates should develop. The chemical Cryst. Monoclinic Monoclinio Rectangular Rhombic
prism prisms plates
properties of the acid (29) with its four functional groups offer
many possibilities for varied uses a t present unexplored.
This investigation was undertaken to evaluate various pro-
posed methods for the synthesis of tartaric acid, and then t o Only the dextro form occurs normally in nature, but upon pro-
determine the possibilities of the best of these for commercial longed heating in water undergoes racemization to the inactive
development. racemic acid Synthetic methods yield racemic or meso-tartaric.
Of the possible starting materials, maleic and fumaric acids acids, the former capable of resolution to yield the two nctivr
were selected as the most suitable, because they are closely re- dextro and levo isomers.
lated t o tartaric structurally and are readily available com-
mercially. They may be easily converted to tartaric acid by PREVIOUS STUDIES
hydroxylation through the following reaction:
The starting materials used in previous investigations of the
HOOC.CH=CH.COOH
Maleic or
+ (0)HOOC.CH(OH).CH(OH).COOH
-I- HzO = synthesis of tartaric acid have been fumaric and maleic acids,
carbohydrates of various types, and in a few cases furfuraldehyde
fumaric acid Tartaric acid ( 2 , 58).
Carbohydrates have been oxidized by nitric acid, usually ~ i t h
Tartaric aeid, containing two hydroxyl and two carboxyl a vanadate catalyst, or by gaseous oxygen under varying condi-
groups attached to an ethane hydrocarbon structure, possesses tions of temperature and pressure and employing a variety of
two centers of asymmetry. It therefore exists in four modifica- catalysts. The best yields of tartaric acid from carbohydrates do
* Present address, National Chemical Research Laboratories, P. 0. Box not exceed 40% of theory with many other acids as by-productp
395, Pretoria, South Africa. (3, 10, 16, 18, 10,41, 41, 66-48). Oxidations of furfuraldehpdc
1780
August 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 1781

have likewise been reported to yield only 45% of tartaric acid by use of Ekkerts color test ( 1 2 ) for detecting tartaric acid by
along with other acids, generally maleic acid (91, 18, 36, 39, 40, means of pyro allol and sulfuric acid. The method of Krauss
and Tampke f . 3 ) was used for a simultaneous detection of
44). tartaric, oxalic, and formic acids, by means of resorcinol and
Tanatar (61) in 1880 first investigated the oxidation of fumaric sulfuric acid. Tartaric acid also was determined quantitatively
and maleic acids by dilute alkaline permanganate, but it was
Kekule and Anschiitz (1, 98) who first showed that this reaction
with fumaric acid gave the dZ-tartaric or racemic acid, while from
maleic the meso acid was obtained. Later Lossen ( 2 4 ) reported
that the addition of hypochlorous acid to fumaric or maleic acid
produced only the monochloromalic acid. The acid potassium
salt of maleic acid, however, could readily be converted into
tartaric acid by boiling water. By a chlorate oxidation of
fumaric and maleic acids in a ueous solution in the presence of
osmium tetroxide, Milas and%erry (34) obtained the racemic
and meso-tartaric acids, respectively, claiming theoretical yields
of 97oJo. Working in tertbutanol solutions of hydrogen peroxide
with osmium tetroxide as the catalyst, Milas and Sussman (38)
hydroxylated maleic acid to obtain 30.3% of meso-tartaric acid
and 48.3% of racemic acid from fumaric acid. Under similar
conditions d-ethyl mesc-tartrate was obtained from diethyl
maleate in 41% yield, and diethyl racemate from diethyl fumar-
ate in 58% yield (9.9, 30, 33). A photochemical addition of
hydrogen peroxide to maleic acid was investigated by Milas,
Kurz, and Anslow ( 3 1 ) under ultraviolet light and resulted in a
9% yield of meso-tartaric acid. Braun (6) further observed the
effects of various chlorates on the oxidation of maleic anhydride
in the presence of osmium tetroxide, which led to a semicontinuous
process (7).
PRELIMINARY INVESTIGATIONS
The oxidizing agents investigated for the hydroxylation of
maleic acid were nitric acid, hypochlorous acid, potassium per-
manganate, aqueous hydrogen peroxide, and gaseous oxygen in
the presence of a catalyst.
PROCEDURES. Essentially the same equipment was used for
all of the hydroxylation reactions with the above agents, and it
is shown in Figure 1.
Maleic anhydride or acid of regular commercial grade was
6rst placed in a threenecked 1-liter flask which was equipped
with ground-glass connections and fitted with an adapter, a glass
stirrer, and a thermometer in the three openings. The adapter
contained a reflux condenser in one of the arms, and a dropping
funnel or gas inlet tube in the other; the oxidizing agent was
added through the latter. An oil or water bath surrounding the Figure 1. Hydroxylation Apparatus
flask waa employed for regulating the temperature of the reaction.
In the case of hydrogen peroxide and hypochlorous acid, after
the addition of the oxidizing agent, the reaction mixture was by adapting the method of Goldenberg (16),which is commonly
refluxed to hydrolyze intermediate addition products: used in analysis of winelees and argols. This method depends
uDon the conversion of tartaric
HOOC.CH=CH.COOH
(Maleic acid)
+ HOC1 +HOOC.CH(OH).CH(Cl).COOH (Chloromaleic acid)
2: tu:&$ft y$t&m ;$
+ \
standard alkali. Inanother sample
HzO HOOC.CH(OH).CH(OH).COOH of the mixed precipitate of calcium
salts oxalic acid was determined

HOOC.CH=CH.COOH + Ha02 +HOOC.CH.CH.COOH

7 (Tartaric acid) according to the method of Isbell
and Holt (8@, by dissolving a
weighed sample in nitric acid and
(Maleic acid) vu reprecipitating the calcium oxalate
(Epoxysuccinic acid) in the p r e s e n c e of a m m o n i u m
acetate, which prevents simultane-
ous precipitation of tartrate. The
This waa not necessary with nitric acid or potassium per-
manganate, as the former was used a t elevated temperatures and
the latter hydroxylation does not a pear to roceed through
an intermediate formation. The cata&ic liquicfphase oxidation TAB^ 11. HYDROXYLATION OF MALEICAND FUMARIC ACIDS
with oxygen was carried out in a standard-type Parr bomb WITH VARIOUS OXIDIZINGAQENTS
hydrogenator. A 100-ml. flask placed within the autoclave
served as a liner to contain the reaction mixture. Upon com- Hypo- Alkaline
pletion of the reaction, the mixture was analyzed and the yield Nitric chlorous Perman- Oxygen Hydrogen
Conditione Acid Acid ganate Aqueous Peroxide
of tartaric acid determined. I n Table I1 the conditions used and
the yields obtained with each oxidizing agent are given. Concn. of re- 50 10 6.5 2001bJ 5 0
agent, % aq. in.
ANALYTICAL METHOD. The reaction mixture was made up to a C o n c s of acids,
given volume and aliquots were analyzed for tartaric and oxalic M&ic 30 6 125 15.6
FGmaric 8
acids. Tern C. 80 10-100 10-80 105 120-100
cata?;at V206 None None WOt WOS
A slight excess of 5% calcium nitrate solution was fkst added 1.0 3.5-7.0 9.6 2.6 6 0
to a hot neutralized sample, followed by addition of ammonium Yield hours
%?me, of ---L 6 1 12 8 300
hydroxide to make the solution slightly alkaline. After heating uct, %
on a steam bath for 1 hour, and standing overnight a t room tem- By-product, % i
perature, a precipitate of the insoluble calcium salts was collected
on a filter, washed, dried, and weighed. These were analyzed
1182 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 43, No. 8
composition of the reprecipitated oxalate was checked by igni- Wiseman (M), but no trace of the hydroxylated compourid could
tion t o calcium oxide and weighing. be detected among the products. Adding the oxygen under pres-
With reaction mixtures containing potassium salts a different
procedure method of analysis was employed. An aliquot of the sure to an aqueous solution of maleic acid, with a variety of
solution was first acidified and chilled t o 5" C. overnight. In- catalysts under a wide range of temperatures and pressures, gave
soluble potassium acid tartrate crystallized out of the solution no evidence of much reaction and no tartaric acid. I n most
and was collected, washed, dried, and weighed. The com- cases the original quantity of maIeic acid was completely re-
position of the salt also was checked by titration. The oxalic
acid remaining in the filtrate was estimated by precipitating the covered unreacted. Of the hydroxylating agents evaluated in
insoluble calcium oxalate in the manner cited above. this preliminary work, hydrogen peroxide seemed to offer the best
Unconverted maleic acid was precipitated as the barium male- possibilities for a practical process. A systematic study of this
ate monohydrate according to the method of Milas and Walsh reaction was therefore undertaken in order t o obtain complete
(%), after removal of tartaric acid as the acid potassium tartrate
and oxalic acid as calcium oxalate. The composition of the information regarding the optimum conditions for highest pos-
barium salt was confirmed by decomposing a weighed sample sible yields of tartaric acid by a hydroxylation of maleic irith
and determining the barium content by the sulfate method ( 4 3 ) . hydrogen peroxide.
An alternative procedure for determining either maleic or
fumaric acid was Szegedy's (60) adaptation of the halogenometric
method of Margosches and Hinner ($6). Under the conditions DETAILED STUDY OF HYDROGEY PEROXIDE REACTION
of the estimation two atoms of bromine add t o the double bond, PROCEDURES. The reaction was carried out using an aqueous
and from the quantity of bromine utilized the concentration of solution of maleic acid or potassium maleate, with potassium
unsaturated acid present may be determined. tungstate as the catalyst. A measured quantity of 35% hydro-
gen peroxide was added to the stirred mixture, and t,he desired
DISCUSSION O F PRELIMINARY RESULTS temperature was maintained for a specified length of time. With
larger batches the equipment described in the preliminary
NITRICACIDREACTIOS. The possibility of reacting nitric acid investigation was used, and a uniform concentration and tem-
with maleic acid to give tartaric acid was examined, using vana- perature maintained throughout the reaction. Heating in this
dium as the catalyet. The reaction was found to be very mild: case was accomplished by using a hot water bath. It was found
advantageous to use slow stirrer speeds t o avoid unnecessary
and the evolution of brown oxide fumes ceased very rapidly. loss of oxygen. The reaction was considered complete when
The effects of temperature over a range of 80" to 110' C., and of the presence of hydrogen peroxide could no longer be detected
nitric acid concentrations from 30 to 700j0,were investigated. in the solution by the standard iodine test (43). At the end of
With higher concentrations and temperatures maleic acid was the reaction tartaric acid and other oxidation products in the
mixture were determined by bhe methods cit,ed previously.
rapidly converted to fumaric acid. Under the optimum condi- When the neutral maleate salt was used, acidification wit'h heat-
tions, only a trace of tartaric was obtained, as shown in Table 11. ing was required t o hydrolyze the intermediate for the liberation
HYPOCHLOROUS ACIDREACTION.Although it was know1 that of tartaric acid. N'hen maleic acid or the acid maleate was
tartaric acids could be prepared from the chlorohydrins of maleic used, heating wit'hout acidification was sufficient for the hydroly-
Y1S.
and fumaric acids, no information in regard to yield had pre-
viously been reported. The best yield of tartrate obtained in this VARIABLES OF REACTION.The effect of catalysts upon the
investigation by this reaction was less than 20% of theory. hydroxylation of maleic acid by hydrogen peroxide is shon-n in
Terry and Eichelberger ( 5 2 ) have shown that the presence of Table 111. A marked increase in. yield was obtained when the
chloride ion in the solution tends to repress the formation of reaction was carried out in the presence of a trace of tungstic arid.
chlorohydrin, and instead favors dichloro addition. This may bc Without any catalyst t'he yields were extremely low (17 ) . TJ.-
the reason for the poor yields. drogen peroxide is known to react with tungstic oxide to form the
POTASSIUM PERMANGANATE REACTION.This reaction was higher unstable pertungstic acids @7), Molybdic acid also
carried out according to Tanatar's (51) method, employing alka- forms compounds of the peracid type with hydrogen peroxitlc,
line permanganate, and resulted in a mixture of acid products. and gave results similar t o those Obtained with tungstic acid,
However, the yield of tartaric acid isolated from the reaction
products was much higher than from either the nitric acid or
hypochlorous acid oxidations. A study of the effect of pH of the
reaction mixture upon the yield of tartaric acid showed that
higher yields were obtained with increasing pH.
HYDROGEN PEROXIDE REACTION.This hydroxylating ageut
has the advantage over most other oxidizing agents of producing
no further oxidation products than the initial hydroxy acid (14 ) ,
but many peroxide reagents do not react with a,@ unsaturated
acids. With tungstic acid as the catalyst, hydrogen peroxide re- REACTION C O N D I T I O N S

- -
acted readily with maleic acid. When the reaction was carried Molar Rotio of Reoctontr 8.0
out in neutral solution, tartaric acid could be detected only after pH of Solution 1.0
Temporotvre- 51%.
the solution had been acidified and boiled for a short period.
This would indicate the formation of an intermediate epoxide
product initially, which upon acid hydrolysis formed t'he hy- 0 I I I I , l I I I L I
droxy acid. It is known that heating a t elevated temperature8 0 0.2 0.4 06 0.8 I.O I,2
CATALYST RATIO
in the presence of acid favors the hydrolysis of an ethylene oxide (Ports WO, per 100 ports Molenc
ring to the dihydroxy derivative ( I S , 49). I n preliminary ex- Anhydride- o r , Gromr W O j per
Grom Mole H y d r o g e n Perortde )
periments yields as high as 30% of theory of tartaric acid were
obtained, with little or no by-product formation, as shown in Figure 2. Effect of Catalyst Ratio on Yield
Table 11.
CATALYTIC OX~DATION WITH OXYGENGAS IN AQUEOUS SOLU- The effects of the quantity of tungstic oxide present in relation to
TION. As hydrogen peroxide appeared to give favorable results hydrogen peroxide and maleic acid are shown graphically in
for the hydroxylation of maleic acid to form the dihydroxy acid, it Figure 2. The yield of tartaric increases very rapidly vith in-
was decided to attempt a similar reaction using gaseous oxygen in crease of catalyst up to 0.4% based upon the weight of maleic
aqueous solution in the presence of a catalyst for preparing the anhydride, after which further additions of catalyst are without
hydrogen peroxide in situ. A first attempt was made in the appreciable effect. The tungstic oxide remaining in solution
vapor phase according to the method of McBee, Haw, and after crystallization of the tartaric acid retains its catalytic.
August 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 1783

activity, as is shown in Table IV. This permits recycling of the I I ] ' I 1 1 '

catalyst contained in the filtrate without addition of fresh

catalyst. However, the catalyst may be easily recovered for
reactivation by addition of hydrochloric acid to the filtrate after
removal of crystallized tartrate salt, thus precipitating the tung-
stic oxide without affecting the unreacted maleic acid left in the
filtrate.

TABLE EFFECTSOF HYDROGEN

111. CATALYTIC PEROXIDE ACT O N CONDITIONS
REACTION
Cat.a HzOz Maleic Maleic/ Tartaricb
Molar Ratio of Reactants : 1.0
Concentration of H20z :
A

3%. 15%
B
-
1.0

Cata- Concn., Concn., Concn., HzOz Tzmz., Yield, 20

I, I<
Maleic Acid : O . 8 M - 4 . 2 M
lyst % % % Ratlo PH % pH of Reaction Solution : 6.0 1.0
None 15
8
50
50
1
2
51
68
1.0
1.0
5.0
6 4
C a t a l y s t R a t i o (WO, based
upon Maleic A n h y d r i d e ) : I% -
1%

0 I I I I I I I I I
0 20 40 60 80 IO0 I20
T E M P E R A T U R E ('C.)

Figure 3. Effect of Temperature on Yield

MOI 1.0 12 38 1 62 2.7 70
1.0 8 20 1 62 1.0 79
WOa (re- 1.0 10 30 1.5 65 1.0 83
used) 1.0 17 40 1 60 1.0 65 very marked decrease. Thiq latter might well be expected in
Basis,weight of maleic,acid. the light of the effect of alkalinity on the decomposition of hy-
Ir Basis, theory maleic acid.
drogen peroxide. When hydroxylation experiments were made
in strongly alkaline solutions, there was an immediate vigorous
TABLEIV. EFFECTOF CONCENTRATIONS PER-
OF HYDROGEN evolution of gas.
OXIDE AND MALEICACIDON TARTRATE YIELD Changes in the initial concentrations of the reactants have
Conditions. Molar ratio of reactants, 1 only a small effect upon the final yield of tartrate, as shown in
Catalyst ratio, 1% WOa based 'upon wei h t of maleic an-
hydride-1 gram WOi per gram mole %ZOZ Table VI; a maximum yield is obtained when 15% hydrogen
Temperature, 57O C. peroxide is used.
PH of reaction solution, 1 Figure 5 shows the importance of molar ratios of reactants for
Time of reaction, 10 hours
Maleic Acid Conon.,
an optimum yield of tartaric acid. Excess hydrogen peroxide
H2O2 Concn., G . Moles/1000 Tartrate" over the stoichiometric amount required has little effect upon the
Expt. No. % M1. Soln. Yield, %
yield, but an excess of maleic acid increases the tartrate yield
considerably. The yield, based on theory of minimum reactant
used, increases steadily with increase in the molal ratio of the
acid from 1 to 1.5, but further amounts of acid have only a small
effect. For optimum conditions a 50% excess of acid is therefore
a Yield calculations based upon theory of hydrogen peroxide consumed, recommended.
Following the course of the reaction by the rate of consumption
of hydrogen peroxide, it is evident from Table V that the major
part of the reaction takes place rapidly; more than 90% of the
Temperature has a marked effect upon the tartrate yields, a8 hydrogen peroxide is consumed within the first 2 to 3 hours.
shown by the results plotted in Figure 3. The results as given This is of considerable importance for the commercial utilization
by curve A were obtained from solutions of neutral potassium of this method of hydroxylation in the production of tartaric acid.
maleate, while those of curve B were obtained from maleic acid ADVANTAGES OF HYDROXYLATION WITH PEROXIDE. This reac-
solutions. Both curves folIow the same trend with a steady in- tion offers good possibilities for a simple method of producing a
crease in yield with increasing temperature, reaching a maximum racemic tartafic acid, utilizing standard procedures and opera-
a t about 70" C., and decreasing rapidly with further
increase in temperature. The optimum temperature
appears to be within the range 60" to 80" C. The

1
fact that the results of curve B are consistently above
those of curve A is in accord with the effects of p H
and of concentration on yield, since B was a t lower
p H and higher concentration than A .
It has been pointed out by Slater (46) that pure
hydrogen peroxide behaves as a weak acid (H+- a
OOH-), and that addition of acid to reduce the p H 2
increases its stability. Increasing the p H much be- b'
40
yond 7.0 results in rapid increase in the rate of 9
w
decomposition. By employing free maleic acid,
potassium acid maleate, neutral potassium maleate,
> Molar R a t i o of Reactcrnfs
Concentration of H,Oz :
I 0
3%
.
+
1.0
15%
or an excess of potassium hydroxide with the neutral " '' Moleic A c i d ILOM I 4.2M
Temparature(Cent,grada). 4s.. 70.
salt, as the starting material to be hydroxylated, a C a t a l y s t R a t i o (W03based
W
P upon M a l e i c Anhydride). 1% 1%
the p H of the reaction solution was varied under L

constant temperature conditions. In Figure 4 the

0
effect of pH on tartrate yields is shown graphically. 0 2.0 4.0 6.0 8.0 0.0 12.0 14.0
Increasing acidity results in a steady increase in pH OF REACTION SOLUTION
tartrate yieM, whereas higher alkalinity results in a Figure 4. Effect of pH on Yield
1784 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 8

ments, a lower price may be expected in the near future. The

TABLEV. RATE OF HYDROXYLATION
OF MALEIC ACID BY stability of high strength hydrogen peroxide likewise has been
HYDROGEN
PEROXIDE greatly improved, and vi-ith proper precautions the material is not
(Based upon rate of consumption of HzOp) hazardous to handle.
Conditions. 35% solution of maleic acid-10% hydrogen peroxide Of academic interest is the fact that this method of hydroxyla-
Molar ratio 1.6 t o 1, temperature 70' C.
tion, in contrast to other hydroxylation reactions, results in a
Elapsed Time,
Hours
0
~-
pH = 1 . 0
100
H A %
pH
100
-
2.7 trans addition of hydroxyl groups t o maleic acid to form the d l acid
isomers. In the reaction with hydrogen peroxide and tungstic
0.5 62.0 40.0 acid there is some evidence of the intermediate formation of an
1.0 41.0 24.0
2.0 19.5 12.7 ethylene oxide ring which undergoes a change in configuration
4.0 5.6 11.1
6.0 2.4 8.6 during hydrolysis (13, $ 7 ) . In other cases of hydroxylation an
8.0 1.4 6.2 intermediate ester product has been poetulated to account for a
10.0 Coinuletelv 4.0
co&umed cis addition which yields the meso-tartaric isomer (9, Si). The
14.0 ".. Completely
consumed chlorate -osmium tetroxide and alkaline permanganate methods
of hydroxylation, because of their stereospecificity, have become
laboratory preparative methods for cis configuration (IC). It is
tions. The hydroxylation is essentially free of undesirable side entirely possible that the hydrogen peroxide-tungstic acid method
reactions and yields a product of high quality directly without may serve equally well as a procedure for trans addition.
purification. I n contrast with other hydroxylating agents, it
PROPOSED CO.MMERCIAL PROCESS .FOR SYNTHESIS
produces a racemic tartaric acid which has the lowest solubility of OF TARTARIC ACID
all the tartaric acids, and therefore can be easily separated from
the reaction solution without an elaborate recovery. Another The process for synthesis of tartaric acid suggested here is
important advantage offered by this method is the recycling of based on the results and procedures developed during this investi-
the catalyst, tungstic acid, which retains its activity, thus per- gation. Although a batch process is suggested, a continuous
mitting its re-use directly after removal of the product from the process would be possible if the volume of production should
reaction solution. Furthermore, the peroxide reaction gives justify it. Although the reaction requires 12 hours for total com-
higher tartaric acid yields than those reported by other synthetic pletion, it is actually over 90% complete within 2 t o 3 hours, and
methods, most of which possess certain inherent disadvantages therefore would permit a continuous method.
causing losses in the yield of tartaric acid due to other oxidation Because of the high acidity of the reaction mixture, and the
reactions, and resulting in an impure product contaminated with tendency of common metallic salts to decompose hydrogen per-
many by-products. In those few cases where the yields are oxide catalytically, it is recommended that glass-lined or aluminum
reasonable, the cost of starting materials and catalyst is high, and reactors be used. As tartaric acid is used as a food and pharma-
t,he purification of the product involved and expensive. ceutical acid, purity of the highest quality is essential, and the use
of noncorrosive equipment is further justified.
100 I I I I I I I i As shown in the flow sheet of Figure 6? maleic acid or its an-
hydride is first dissolved in water to give a solution of about
0
-
CONDITIONS
- 30% concentration, and the required amount of catalyst solution,
in the form of a dilute solution of potassium tungstate, is added
'
V Solution p H e 2.7
- to provide 0.5% tungstic oxide, based upon the weight of maleic
used. The hydrogen peroxide is added t o the mixture in the
form of the 35y0 commercial strength product, which upon dilu-
tion by water used in the reaction mixture gives a hydrogen
peroxide concentration of about 15% in the reaction solution.
The amount of reactants is in the ratio of 1.5 moles of maleic
to 1 of peroxide, thus providing a 50% excess of the maleic.
By supplying warm water t o the jacket of the reactor, a
reaction temperature of 70" C. is maintained throughout the
reaction period. The reactor should be provided with a con-
ventional-type stirrer, a temperature-recording device, a suitable
reflux condenser, and a sampling device. When nearly complete
consumption of peroxide shows the reaction to be finished, the
temperature is slowly increased and the reaction mixture in
brought to reflux temperature for about 1 hour to msure com-
plete hydrolysis of the intermediate epoxy compound for the
formation of tartaric acid. The total time required for a com-
plete reaction is about 12 hours; a 90% completion is obtained
50 within 3 hours.
0 0.5 I.o 1.5 2.0
Following the reaction, the mixture is cooled and then dis-
MOLAR RATIO OF REACTANTS (Moleic/H,OzR
Figure 5 . Effect of Ratio of R e a c t a n t s on
Yield
TABLEVI. MATERIALREQUIREMEKTS FOR SYNTHETICTAR-
OF 1000 P O U N D S O F A4NHYDROUSTARTARIC
TARIC ACIDPER BATCH
Over-all process costs would therefore be much higher than in ACID
the hydrogen peroxide process, where a high quality product is Maleic anhydride, Ib.
Fresh 673
easily recovered from the reaction mixture, permitting the re- From recycle solution 487
cycling of catalyst and any unreacted starting material for a Total maleic 1160 (437
solution)
gallons of 30%
greater economy. The main concern in the use of hydrogen Catalyst contained in reoycle solution, lb.
Tungstic oxide 5.8
peroxide for the hydroxylation of maleic to tartaric acid is the Potassium hydroxide 2.9
cost of the hydrogen peroxide, which is a determining factor in Hydrogen peroxide, 35% solution 770 (93 gallons)
the final cost of the synthetic tartaric acid. As a result of in- Yields, %
creased hydrogen peroxide production during World War I1 (8), Conversion of maleia acid 58
Theory, on maleic consumed 97
this chemical is now available at a reasonable price in high Theory, on peroxide used 84
atrength concentrations, and with continued market develop-
August 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 1785
unreacted starting material were obtained. The yield of tar-
taric acid was only %yo of theory.
Catalytic oxidation, employing gaseous oxygen with a variety
of catalysts under varying conditions, gave no trace of tartaric
acid, and resulted in most cases in complete recovery of the
starting material.
Hydrogen peroxide, with tungstic acid as the catalyst, gave
TANK
the best yields of tartaric acid without any apparent side products.
n ( I X C a t olyst Soln.)
As a result of these evaluations, hydrogen peroxide with tung-
stic acid aa the catalyst was studied in detail, and the optimum
conditions for a maximum yield of tartaric acid from maleic acid
were established.
Tungstic acid proved t o be the preferred catalyst when used
in concentrations of over 0.5% based upon the wei h t of maleic
acid present. Furthermore, tungstic acid is easiyy recovered
from the reaction products and may be re-used several times
without reactivation.
I
CRYSTALLIZER
Temperatures of about 70 O C. gave the highest conversiona
and yields.
The maleic acid, or acid salt, representing a low p H reaction
5%. mixture, gives much better results than the neutral maleate
salt or an alkaline medium. The latter causes a rapid decom-
position of the hydrogen peroxide and consequent loss in yield.
Concentration of the reactants appears to have little or no
effect upon the yield of tartaric acid. Slightly better results
were obtained when 30% maleic acid was used with 15% hydro-
gen peroxide for the reaction.
A 50% excess of maleic acid over the stoichiometric amount
DRIER- IlOC. required gave an increased yield of tartaric acid based upon both
I
the acid and the peroxide consumed.
The reaction is rapid, over 90% of the hydrogen peroxide
being reacted within the first 2 to 3 hours. For a complete
TARTAR I C reaction, however, a minimum of 10 to 12 hours is required.
+ I H,O I (Anhydrous] I Under the optimum conditions a 957, theory yield of racemic
tartaric acid with a 58% conversion of maleic acid is obtained.
Based upon the total hydrogen peroxide used, the theory yield ie
Figure 6. Flow Sheet of Proposed Process 84%. The tartaric acid obtained directly by crystallization from
the reaction mixture is of extremely high quality. A commercial
charged to a crystallizer, where it is further chilled with refriger- process for the synthesis of tartaric acid from maleic acid based
ated water to a low temperature over a eriod of several hours to upon these results has been suggested.
obtain a complete crystallization of t f e acid. The slurry re-
sulting is sent to a centrifuge, where the crystals of tartaric acid
are removed from the saturated filtrate, and are washed rapidly LITERATURE CITED
with a small amount of cold water. The tartaric acid is then (1) Anachtita, R., Ann., 226, 191 (1884).
dried a t about 60 C. for the monohydrate or a t 110 C. for the (2) Baekeland, L. H., and Peter, A. H., U. S. Patent 1,190,846
anhydrous acid. The product is of sufficiently high quality (1916).
requiring no further purification for commercial use or for con- (3) Barch, W.E., Ibid., 2,417,230(1947).
version to other tartrate products by neutralization to cor- (4) Black, J. W.,I d . Chemist, 14, 433-4 (1938).
responding salts. The raw material requirements, per 1000 (5)Ibid., 15, 270-1 (1939).
pounds of anhydrous tartaric acid, are given in Table VI, along (6) Braun, G., J . Am. Chem. SOC.,51, 228-48 (1929).
with the average yields based upon maleic and hydrogen peroxide (7) Braun, G.,U. S. Patent 2,000,213(1935).
consumed in the reaction. (8) Cooley, R. A.,Chem. I d s . , 58, 957-61 (1946).
The saturated filtrate, containing some dissolved tartaric acid, (9) Criegee, R.,Ann., 522, 75 (1936).
catalyst, and unreacted maleic, is recycled to the next batch. (10) Dale, J. K., and Rice, W. F., Jr., J. Am. Chem. SOC.,55,4984-6
Maleic anh dride or acid is added to replace that converted to (1933).
tartaric a c i t and the required amount of 35% peroxide is charged (11) Dyson, G. M.,Chem. Age (London),20, 331-3 (1929).
for the production of a second batch under the same conditions (12) Ekkert, L.,Pharm. Zentralhalle, 66, 765 (1925).
as in the first batch. The catalyst, which ia in the form of a (13) English, J., Jr., and Gregory, J. D., J. Am. Chem. SOC..69,
soluble tungstic acid complex, retains its activity, and may be 2120-2 (1947).
recycled several times before renewal is necessary. After several (14) Fieser, L. F., and Fieser, M., Organic Chemistry, pp. 66,
batches it may be advisable to recover the soluble catalyst for 253-6. Boston. D.C. Heath and Co.. 1944.
reactivation by precipitation, following acidification of the filtrate (15) Goldenberg, Gerornont and Co., 2. anal. Chem., 37, 312, 382
with hydrochloric acid. A fresh catalyst solution is prepared, (1898).
free of any accumulated impurities, by redissolving the precipi- (16) Hales, R.A., U. S. Patents 2,419,019,2,419,020(1947).
tated tungstic acid in dilute alkali. (17) Hatcher, W.H., and Mueller, W. H., Can. J . Research, 3, 291-
305 (1930).
SUMMARY AND CONCLUSIONS (18) Henaerling, H.L.,U. S. Patent 1,834,057(1931).
(19) Hill, G. A.,and Kelly, L., Organic Chemistry, p. 391,Phila-
This investigation was first concerned with the evaluation of delphia, Blakiston Co., 1944.
several hydroxylating agents for possible use in the synthesis of (20) Isbell, H. S., and Holt, N. R., J. Research Natl. Bur. Standards,
tartaric acid from maleic acid. It was found that: 35, 433-8 (1945).
(21) Jaeger, A. O.,U. S. Patent 1,995,614(1935).
Nitric acid oxidation of maleic acid did not yield any detectable (22) Kekul6, A., and Ansohiits, R., Ber., 13, 2150 (1880); 14, 713
amount of tartaric acid in the reaction products, and gave only (1881).
oxalic acid of a low yield as the main product. (23) Krauss, F.,and Tampke, H., Chem.-Ztg., 45, 521 (1921).
Hypochlorous acid gave very low yields of tartaric acid, less (24) Lossen, W., Ann., 348,273 (1906).
than 20% of theory. Direct chlorination as a competing reaction (25) McBee, E. T.,Hass, H. B., and Wisernan, P. A,, IND. ENG.
was believed responsible for these low yields. CHEM.,37, 432-8 (1945).
The reaction with alkaline permanganate gave a mixture of (26) Margosches, B. M.,and Hinner, W., Z. anal. Chem., 64,61-72
acid products from which oxalic and tartaric acids tw well as (1924).
1786 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 43, No. 8

(27) bIeilor, J. W., Comprehensive Treatise on Inorganic and 5th ed., pp. 127, 2180, New York, D. Van Nostrand Co.,
Theoretical Chemistry, Vol. XI, pp. 734, 833, London, 1938.
Longmans, Green and Co., 1931. (44) Sessions, W. V., J . Am. Chem. SOC.,50, 1696-8 (1928).
(28) Milas, N. A., J . Am. Chem. Soc., 49, 2005-11 (1927). (45) Slater, V. W., ChemistrzJ and I n d u s t r v , 1945, No. 6, 42-6.
(29) Ibid., 59, 2342-4, 2345-7 (1937). (46) Soltzberg, S., U. S. Patent 2,380,196 (1945).
(30) Milas, N. A., U. S. Patents 2,402,566 (1946); 2,414,384 (1947); (47) Stokes, W. E., and Barch, W. E., Ibid., 2,257,284 (1941).
2.437.648 (1948). (48) Stokes, W. E., and Peter, A. H., Ibid., 1,870,472 (1932).
(31) Milas, N. A:, Kurs, P. F., and Anslow, W. P., Jr., J . Am. (49) Swern, D., Billen, G. N., Findley, T. W., and Scanlan, J. T.,
Chem. SOC.,59, 543-4 (1937). J . Am. Chem. Soc., 67, 1786-9 (1945).
(32) Milas, N. A., and Sussman, S., Ibid., 58, 1302-4 (1936). (50) Szegedy, E., Z . anal. Chem., 109, 95-107 (1937).
(33) Milas, N. A,, Sussman. S..and Mason. H. S.. Ibid.. 61, 1844-7 (51) Tanatar, S., Ber., 12, 2293 (1879); 13, 1383 (1880).
(1939). (52) Terry, E. M., and Eichelberger, L., J . Am. Chem. Soc., 47,
(34) Milas, N. A., and Terry, E. bI., Ibid., 47, 1412-18 (1925). 1067-77 (1925).
(36) Milas, N. A., and Walsh, W. L., Ibid., 57, 1389-93 (1935). (53) Thorpe, J. F., Dictionary of Applied Chemistry, 3rd and
(36) Milas, N. A,, and Walsh, W. L., U. S. Patent 2,118,567 (1938). 4th eds.. London, Longmans, Green and Co., 1927 and 1937.
(37) Mugden, M., and Young, D. P., J. Chem. SOC.,1949, 2988-
8000. RECEIVED September 1.3, 19.30. Presented before the Division of Industrial
(38) Newman, A. C. C., and Riley, H. L., Ibid., 1933, 45-6. and Engineering Chemistry, Fifteenth Unit Proceas Symposium, a t the
(39) Nielaen, E. R., IND. ENG.CHEW., 41, 365 (1949). 118th Meeting of the AMERICANCHBMICAL SOCIBTY, Chicago, 111. Based
(40) Nielsen, E. R., U. S. Patent 2,421,428 (1947). on a thesis presented to the Department of Chemical Engineering, Columbia
(41) Pasternack, R., and Brown, E. I-.,Ibid., 2,197,021 (1940). University, in partial fulfillment of the requirementa for the Ph.D. degree,
(42) Sanders, M. T., Ibid., 2,419,038 (1947). June 1949. Contribution No. 18 from Chemical Engineering Laboratories,
(43) Scott,. A . W., Standard Methods of Chemical Analysis, Columbia University, N. Y.

Degradation Rate of
Cellulosic Pulps
R. L. MITCHELL
Rayonier Znc., Shelton, Wash.

T h e viscosity of viscose produced from various celluloses 1 1 droxide

~ all the way down to a near-zero concentration,
under standardizedprocessing conditions is not dependent even though the abrupt rise in aging reactivity does occur
alone on initial degree of polymerization, but is further in- above 7Yo sodium hydroxide. A further modification of
fluenced by the rate of cellulose degradation. A simplified the procedure in which 290 sodium hydroxide is used pro-
procedure for quickly evaluating degradation rate so that vides the means for revealing prior treatment of the cellu-
it may be expressed in a single numerical term is desirable. lose with relatively strong solutions of sodium hydroxide.
The degradation increase is shown to be a specific and The measurement of degradation increase offers a new
characteristic property of the cellulosic material. The approach to the study of alkali cellulose aging by providing
dependence of aging requirement on degradation rate and a single numerical term for expressing rate of alkaline
on initial degree of polymerization is illustrated by oxida- oxidative degradation. Degradation rate measurements
tive degradation measurements on a variety of celluloses. supplement initial degree of polymerization values in re-
Variation of the procedure shows that cellulose is con- flecting the aging requirements of widely varying types of
tinuously changed (in a sense mercerized) by sodiuni cellulosc.

I K PROCESSING dissolving-type celluloses into viscosec

celluloses of similar viscosity do not always yield viscose s o h -
tions of correspondingly similar viscosity. The deviations in
characteristic differences, a proximate parallelism with equilib-
rium moisture content.
The measurement of degradation increase offers a new approach
viscose viscosity which may occur for different types of cellulosic to the study of alkali cellulose aging by providing simple numeri-
pulps of similar degree of polymerization appear to be due in cal terms for expressing the rate of alkaline oxidative degradation
large meamre to differences in the aging characteristics of the (hond cleavage).
celluloses. The viscosity of viscose produced under standardized
mocessine: conditions is not dependent alone on initial degree of EXPERIMEXTAL
polymerigation but is further influenced by the rate a t which the
A G I N G P R O C h D L R E FOR DETERMISING
DEGRA1)ATION R A T E .
degrades+ This rate Of degradation in turn may The standardized accelerated aging procedure for determining the
influenced by contamination of the p u b with small amounts of rate of degradation or aging reactivity is based on the measure-
certain metal ions such as iron and manganese ( 8 ) . ment of the degradation increase which occurs when alkali cellu-
The rate of alkaline oxidative degradation, as measured by the lose aged for 2 hours at 50 C. in oxygen. In the method, a 10-
degradation increase which occurs when alkali cellu]ose is sub- P a m sample of cellulose is slurried at 2.5% consistency in an
18.0% aqueous solution of caustic soda a t 20 C. and allowed to
jected to a standardized accelerated aging treatment, is a specific stand for 10 minutes. The slurry is then at about
and characteristic property of cellulose and may be used a,s a 600 G to give a weight of about 35 grams. The centrifuged alkali
valuable adjunct to degree of polymerization in predicting aging cellulose is weighed and split into two portions. One portion is
requirement and xanthate solution viscosity. Furthermore, recovered immediately in dilute sulfuric acid (50 grams per liter)
and later washed acid-free. The second portion is quickly (2
measurement of degradation rate provides a m,eans for indicating seconds) disintegrated in an Osterizer, in a suitable 4.
relative degree of mercerization and shows, aside from certain ounce plastic capped bottle, flushed carefully with oxygen, sealed,