PRODUCTION OF SODIUM BENZOATE

There are three methods for the commercial preparation of sodium benzoate.

1) In one method, naphthalene is oxidized with vanadium pentoxide to give

phthalic anhydride. This is decarboxylated to yield benzoic acid.
2) In a second method, toluene is mixed with nitric acid and oxidized to
produce benzoic acid.
3) In a third method, benzotrichloride is hydrolyzed and then treated with a
mineral acid to give benzoic acid. Benzotrichloride is formed by the reaction
of chlorine and toluene. In all cases, the benzoic acid is further refined to
produce sodium benzoate.

One way this is done is by dissolving the acid in a sodium hydroxide solution.
The resulting chemical reaction produces sodium benzoate and water. The crystals
are isolated by evaporating off the water.

The Chemistry of Sodium Benzoate

Sodium benzoate is the sodium salt obtained when benzoic acid reacts with sodium
hydroxide. This is an acid-base reaction that produces a salt, which is sodium
benzoate, and water. The chemical formula is:

C7H6O2 + NaOH = NaC7H5O2 + H2O

In water, the compound dissolves and dissocates into a sodium ion and a benzoic acid
ion. In its solid form it is a white, granular or crystalline powder that can be added to
food or cosmetics.

Granular sodium benzoate and its production process

The present invention is granular sodium benzoate and its production

process. The production process includes the neutral reaction between
benzoic acid and sodium hydroxide inside a neutralizing tank at pH 7.5-8.0
and 95-98 deg.c for 30-40 min to produce crude sodium benzoate solution;
decolorizing the crude sodium benzoate solution with active carbon for 40-
45 min, and filtering at the pressure of 0.3-0.4 MPa to obtain clean sodium
benzoate solution; and palletizing, drying and packing to obtain granular
sodium benzoate in the shape of 1.5-2 mm ball. Producing granular sodium
benzoate has simplified production of the downstream product, improved
work condition and expanding application range.

Granular sodium benzoate and production method

Technical field

The invention belongs to organic chemical industry's product and preparation

method, particularly granular sodium benzoate and production method.

Background technology

Sodium Benzoate claims sodium benzoate again, molecular formula:

C 7H 5NaO 2The powdery that is white in color, have sterilant, the fuel industry of
sanitas that sweet astringent taste, water-soluble and ethanol be mainly used in
foodstuffs industry, medicine industry mordant, plastics industry softening agent
and be the manufacturing raw material of spices.Quality product meets the
GB1902-2005 standard.The powdery Sodium Benzoate is one of conventional
sanitas that uses in the foodstuff additive, because the flowability of powder-like
product is poor, storing, hardens easily again in the transportation.When derived
product is used, need pulverize, cause manpower again, the waste of the energy
and the pollution of environment.

Summary of the invention

At these defectives of the powder-like product of prior art, we have developed
granular sodium benzoate and production method.

Granular sodium benzoate provided by the invention is shaped as the spherical

shape body, and diameter is 1.5～2mm.

The production method of granular sodium benzoate of the present invention is:
phenylformic acid and sodium hydroxide are put in the neutralization tank, carry
out neutralization reaction at neutralization tank, pH value is controlled at 7.5～
8.0, and temperature of reaction is: 95～98 ℃, reaction times: 30 ~ 40min carries
out neutralization reaction fully; Generate thick matter Sodium Benzoate solution
and add gac and decolour, bleaching time 40～45min is to filter under the
condition of 0.3～0.4Mpa at filter pressure, obtains clean Sodium Benzoate
solution.

The part by weight of phenylformic acid and sodium hydroxide is 3: 0.8～1.5.

Sodium Benzoate solution after filtering is passed through granulation, drying and
is packaged to be diameter is that 1.5～2mm Sodium Benzoate is shaped as the
spherical shape body.

Granulation is that the Sodium Benzoate solution after filtering is carried liquid
sodium by equally distributed 4～6 nozzles in prilling tower, carries air by these
nozzles in tower simultaneously, tower inner control temperature in 145 ℃～150
℃ scope, air inlet amount: 6～8m 3/ min, the control intake pressure is at 0.3～
0.4Mpa.

In tower, place grain sodium crystal seed.Drying is the oven dry 150～155 ℃ of
temperature.But product can produce little electrostatic phenomenon when
adopting the plastic inner lining packaging bags, thereby should adopt paper bag
packing when packing this product.

Granular sodium benzoate of the present invention is shaped as the spherical

shape body, and is easy in use laborsaving, and phenomenon does not harden in
transportation, storage process.

Effect of the present invention:

(1) production technique:

Particulate state phenylformic acid production technique and powdery Sodium

Benzoate production technique relatively have: raw materials consumption is low,
characteristic of low energy consumption.Particular case sees the following form

Unit product consumption contrast

Vapour 3 ?5 -2 Gac 2kg ?3kg -1kg Packing bag Article 15, Article 40, Article-25,

(2) because of effect comparison that product form produced Product
form Granular sodium benzoate. The powdery Sodium Benzoate The effect that
produces Good fluidity does not harden Mobile poor, the phenomenon of
hardening is arranged No dust pollution Dust pollution is arranged Raw material
consumption is low The raw material consumption height Energy consumption is
low The energy consumption height Product purity, content, color and luster are
stablized Product purity, content, color and luster instability The broadened
application field Application Areas does not enlarge, and market has by granular
sodium benzoate occupies trend Produce micro-static (adopting paper wrapping
bag to solve) There is not micro-static Produce and be hermetically sealed
form Production is half open form

The invention of granular sodium benzoate production technique, changed the

high defective of raw material consumption height, the energy consumption of
powdery Sodium Benzoate production technique, make quality product obtain
stable with improve, not only meet the GB1902-2005 standard, and meet the
quality standard of British Pharmacopoeia 2000 editions.

The Sodium Benzoate product changes particulate state into by powdery, the
operation that derived product is produced has been simplified in the invention of
this product form, save human and material resources and made work situation,
labor condition that basic improvement arranged, improved the safety operation
performance, enlarged the Application Areas of Sodium Benzoate product.

Embodiment

Embodiment 1:

Technical benzene formic acid 850kg with 〉=98.0% and 32% sodium hydroxide
860kg put into neutralization tank, carry out neutralization reaction at
neutralization tank.PH value is controlled at 7.5, and temperature of reaction is:
95 ℃, and reaction times: 40min, neutralization reaction is carried out the back
fully and is generated thick matter Sodium Benzoate solution; In bleacher, add gac
5～15kg, bleaching time 45min, operation after filtration, controlled filter
pressure is 0.3Mpa, obtains clean Sodium Benzoate solution; Sodium Benzoate
solution is carried liquid sodium by equally distributed 4 nozzles in prilling tower,
simultaneously in tower, carries air by these 4 nozzles, tower inner control
temperature in 145 ℃ scope, air inlet amount: 6m 3/ min, control intake pressure
are at 0.3Mpa, and the grain sodium crystal seed of the 25kg in making the liquid
material and being placed on tower in advance contacts in the tower bed
repeatedly, and form the granular sodium benzoate of 1.5～2mm standard, and
output is about 500kg.After be packaged as finished product after the oven dry of
150 ℃ of temperature, screening.

Embodiment 2:

Technical benzene formic acid 850kg with 〉=98.5% and 30% sodium hydroxide
916kg put into neutralization tank, carry out neutralization reaction at
neutralization tank, pH value is controlled at 8, and temperature of reaction is: 98
℃, reaction times: 30min, neutralization reaction is carried out the back fully and
is generated thick matter Sodium Benzoate solution; According to the colourity
situation of thick matter Sodium Benzoate solution, in bleacher, add gac 5 ~ 15kg,
bleaching time 45min, operation after filtration, controlled filter pressure is
0.4Mpa, Sodium Benzoate solution; Sodium Benzoate solution is carried liquid
sodium by equally distributed 6 nozzles in prilling tower, simultaneously in tower,
carries air by these 6 nozzles, tower inner control temperature in 150 ℃ scope, air
inlet amount: 8m 3/ min, control intake pressure make the liquid material contact
repeatedly in the tower bed with a sodium crystal seed that is placed on the 50kg
in the tower in advance at 0.4Mpa, and the granular sodium benzoate output that
forms 1.5～2mm standard is about 800kg.After be packaged as finished product
after the oven dry of 155 ℃ of temperature, screening.

Embodiment 3:

Technical benzene formic acid 850kg with 〉=98.5% and 25% sodium hydroxide
921kg put into neutralization tank, carry out neutralization reaction at
neutralization tank, pH value is controlled at 8, and temperature of reaction is: 98
℃, reaction times: 35min, neutralization reaction is carried out the back fully and
is generated thick matter Sodium Benzoate solution; According to the colourity
situation of thick matter Sodium Benzoate solution, in bleacher, add gac 5 ~ 15kg,
bleaching time 45min, operation after filtration, controlled filter pressure is
0.35Mpa, Sodium Benzoate solution; Sodium Benzoate solution is carried liquid
sodium by equally distributed 5 nozzles in prilling tower, simultaneously in tower,
carries air by these 5 nozzles, tower inner control temperature in 155 ℃ scope, air
inlet amount: 8m 3/ min, the control intake pressure is at 0.4Mpa, a grain sodium
crystal seed that makes the liquid material and be placed on the 30kg in the tower
in advance contact in the tower bed repeatedly, and the granular sodium
benzoate output that forms 1.5～2mm standard is about 600kg, after the oven
dry of 152 ℃ of temperature, screening back with paper for being packaged as
finished product.

Claims (7)

Hide Dependent 

1. a granular sodium benzoate is characterized in that Sodium Benzoate is shaped

as the spherical shape body, and diameter is 1.5～2mm.
2. the production method of granular sodium benzoate as claimed in claim 1, the
production method that it is characterized in that granular sodium benzoate is:
phenylformic acid and sodium hydroxide are put in the neutralization tank, carry
out neutralization reaction at neutralization tank, pH value is controlled at 7.5～
8.0, temperature of reaction is: 95～98 ℃, reaction times: 30 ~ 40min carries out
neutralization reaction fully; Generate thick matter Sodium Benzoate solution
adding gac and decolour, bleaching time 40～45min is the condition filter of 0.3～
0.4Mpa at filter pressure, obtains clean Sodium Benzoate solution.
3. the production method of granular sodium benzoate as claimed in claim 2, the
part by weight that it is characterized in that described phenylformic acid and
sodium hydroxide is 3: 0.8～1.5.
4. the production method of granular sodium benzoate as claimed in claim 2 is
characterized in that the Sodium Benzoate solution after filtering through
granulation, drying with to be packaged to be diameter be that 1.5～2mm
Sodium Benzoate is shaped as the spherical shape body.
5. the production method of granular sodium benzoate as claimed in claim 2, it is
characterized in that described granulation is to carry liquid sodium to carry air by
these nozzles in tower simultaneously by equally distributed 4～6 nozzles the
Sodium Benzoate solution after filtering in prilling tower, tower inner control
temperature in 145 ℃～150 ℃ scope, air inlet amount: 6～8m 3/ min, the control
intake pressure is at 0.3～0.4Mpa.
6. the production method of granular sodium benzoate as claimed in claim 5 is
characterized in that described drying is the oven dry 150～155 ℃ of
temperature.
7. the production method of granular sodium benzoate as claimed in claim 4 is
characterized in that described packing adopts paper bag packing.

uses
Sodium benzoate is a food preservative that occurs naturally in some fruits. The
chemical is the sodium salt of benzoic acid and is considered safe to ingest and apply
to the skin. It should not be used in certain acidic products because it may combine to
form harmful compounds, but it is not toxic and does not irritate tissue. It dissolves
readily in water, and its primary use is to inhibit the growth of molds and bacteria in
food and cosmetics.

Sodium benzoate keeps molds and bacteria from growing in food and cosmetics. It is
found in many fruit drinks, in salad dressings and oils, and in jams. Cosmetic
manufacturers use it in skin creams and other cosmetics to keep them fresh. It is
found naturally in fruits such as plums and cranberries and in spices such as
cinnamon. Use of the chemical is widespread because it is inexpensive and because
small concentrations, typically 0.05 - 0.1 percent, are effective.

In solution, the benzoic acid ion is the active ingredient and acts directly on micro-
organisms to limit their activity. When used in certain foods such as acid citrus drinks,
the sodium benzoate may react with the other acids such as citric or ascorbic acids to
form benzene, a potential carcinogenic compound. Because the levels of sodium
benzoate in most foods are so low, the corresponding concentration of benzene will
also be below dangerous levels. In general, sodium benzoate is a safe, common,
inexpensive and effective food additive with possibly some restrictions for a high
consumption of certain acid foods.

Production OF BENZOIC ACID

There are three main industrial production methods for the synthesis of benzoic acid now, namely,

1) the liquid-phase air oxidation of toluene,

2) the hydrolysis of trichlorotoluene.
3) the decarboxylation of phthalic anhydride

4) Toluene can be oxidized to several oxygenates like benzoic acid, benzaldehyde, and benzyl alcohol [15-18],
and the yield of a desired product derived from the oxidation process depends on catalysts, oxidizers and
reaction conditions [16, 19]. For example, the gas-phase catalytic oxidation of toluene [20, 21] and the liquid-
phase catalytic oxidation of toluene [16-19], have been developed for producing benzoic acid or
benzaldehyde. The gas-phase catalytic oxidation of toluene was usually performed at middle temperature
using air or oxygen as oxidants over transition metal oxide catalysts (like vanadium oxide, iron oxide and
 cobalt oxide) or composite metal oxide catalysts [20-23]. The gas-phase oxidation process is more favorable
for simplifying product separation process as compared with liquid-phase catalytic oxidation process, but
has some disadvantages including lower selectivity of benzoic acid or benzaldehyde, and the deactivation of
the catalysts [20, 24].

5) Alternatively, the liquid-phase catalytic oxidation of toluene to benzaldehyde and benzoic acid has also
attracted much attention [14-16, 19, 25]. Typically, soluble metal salts like cobalt or manganese-based
halides are used as catalysts for the liquid phase oxidation of toluene, together with the addition of bromide
as a catalyst promoter [26, 27]. The bi-metallic catalysts [28], metal complex catalysts [29], and metal-
molecular sieve composite catalysts [15, 18, 30] have also been investigated for the liquid phase catalytic
oxidation of toluene.

6) Herein, the production of benzoic acid from lignocellulosic biomass (sawdust) was achieved by a proposed
transformation process under atmospheric pressure, giving the high selectivity of the targeted product
(benzoic acid).

7) C. Oxidation of toluene-rich aromatics

8) Finally, the synthesis of benzoic acid was performed by the low-temprature liquid-phase oxidation of the
toluene-rich aromatics (namely CDO) using oxygen as an oxidant. The different catalysts, including MnO22,
NHPI, MnO22/NHPI, CoCl22/NHPI, MnCl22/NHPI and CuCl22/NHPI, have been investigated for the
oxidation of CDO to benzoic acid. As can be seen from Table Ⅱ, the MnO22 catalyst shows very low
oxidation activities of aromatics. Adding the promoter of NN-hydroxyphthalimide (NHPI) into the reaction
system (MnO22/NHPI) effectively enhanced the catalytic activities for the oxidation of CDO, especially for
the oxidation of toluene and xylenes. The conversion of toluene reached 87.1 C-mol% under the typical
condition (80 ℃℃, 4 h) using MnO22/NHPI, and the main products obtained were benzoic acid and toluic
acid with the selectivity of 77.7 C-mol% and 14.0 C-mol% respectively. NHPI could mainly play a key role as
an initiator or promotor in the oxidation of aromatics, similar to the previous investigation on the oxidation of
alkanes [37]. Moreover, the catalysts containing the transition metal halide such as CoCl22/NHPI,
MnCl22/NHPI, and CuCl22/NHPI also exhibited high activities for the CDO oxidation. However, these
catalysts may be environmentally harmful because of halide-containing compositions. Accordingly,
MnO22/NHPI was selected for the production of benzoic acid, which was investigated in details under
different conditions.

Industrial preparations

Benzoic acid is produced commercially by partial oxidation of toluene with oxygen. The

process is catalyzed by cobalt or manganese naphthenates. The process uses cheap raw
materials, proceeds in high yield, and is considered environmentally attractive.
C7H8 + 02

U.S. production capacity is estimated to be 126 000 tonnes per year, much of which is
consumed domestically to prepare other industrial chemicals.

Method 1
A process for the manufacture of benzoic acid is described. The process is based on the reaction of
toluene in a liquid phase oxidation with an oxygen containing gas in the presence of a phase-transfer
catalyst (a), a transition metal salt (b) and traces of a polar solvent, such as water, the molar ratio
between (a) and (b) being in the range of between 0.25:1 to 1.5:1. The phase-transfer catalyst is
selected from quaternary ammonium and phosphonium salts having a total carbon atoms in the range
of 17 to 58, the anion bound thereto being selected from Br -, F-, Cl-, OH-, CH3 COO- or HSO4 -. The benzoic
acid produced is characterized by its very high purity and high conversion reaching generally values of
above 95%.

Recycling of waste from sodium benzoate

Industrial residues formed in the industrial production of benzoic acid by cobalt-
catalyzed oxidation of toluene are traditionally disposed as waste materials and often
burnt or buried. It therefore may become a significant source of environmental
pollution. In this report, we describe simple techniques to obtain high value conjugated
aromatic compounds, including 9-fluorenone, 6H-benzo[c]chromen-6-one, biphenyl-3-
carboxylic acid, and biphenyl-4-carboxylic acid, from benzoic acid industrial residue
using inexpensive alkalis and acids. The separation methods involve simple and mild
procedures with high economic effectiveness and low environmental contamination.

Classifications

Jun 1, 1965 J. G. HUNDLEY CONTINUOUS OXIDATION PROCESS FOR PRODUCTION OF BENZOIC

ACID Filed Jan. 9, 1961 ATTORNEY United States Patent 3,187,038 CONTINUOUS @XIDATION
PRUQESS FOR PRODUCTION GF BENZGIC ACED John G. Hundley, Munster, Ind, assignor to
Standard (Bil Company, Chicago, Ill., a corporation of Indiana Filed Jan. 9, 1961, Ser.
No. 81,559 2 Claims. (Cl. 260-524) This invention relates to an improved process for the
preparation of benzoic acid. More particularly, the invention is concerned with an
integrated, continuous process for the conversion of toluene to benzoic acid by catalytic
liquid phase air oxidation in the presence of metal oxidation catalysts, and with means
for effecting efi'icient recovery of high purity benzoic acid suitable for commercial
applications.

Heretofore it has been known to produce benzoic acid by the oxidation of toluene With
an oxygen-containing gas in the presence of a heavy metal oxidation catalyst, for
example cobalt and/or manganese salts. Such oxidations, whether effected batchwise
or by continuous processes, have generally been etiected in the presence of a reaction
solvent or medium, such as a lower saturated aliphatic carboxylic acid or in the
presence of an excess of reactant, namely, toluene, which serves as reaction medium
diluent, as well as feedstock in the oxidation process. It has hitherto been proposed that
benzoic acid, which is itself the desired product of reaction, be employed as a reaction
medium for effecting toluene oxidation to benzoic acid.

The object of this invention is to provide an improved commercial oxidation system

which is particularly suitable for the conversion of toluene to benzoic acid and which
employs benzoic acid as a reaction medium. A further object is to provide a novel
continuous oxidation system Which will result in the attainment of product quality and
yields comparable or even superior to those attainable by batch processes. A further
object is to provide an integrated system for separating benzoic acid from a recycle
stream comprising benzoic acid, catalyst and associated impurities most effectively.
These and other objects will be apparent as the detailed description of the invention
proceeds.

In practicing the invention, fresh toluene charging stock is introduced into the lower part
of a continuous oxidation reactor which contains a large body of benzoic acid reaction
medium. An important aspect of the invention is the control of the concentration of
toluene in the reactor below about 5% and preferably below about 2% by weight based
on the benzoic acid employed as reaction medium. In order to maintain this low
concentration of toluene, the reaction mixture consisting primarily of benzoic acid is
withdrawn continuously from the top of the reactor and recycled continuously to the
bottom thereof, means being provided for the continuous separation of a slip stream of
benzoic acid from the recycle stream. The oxygen-containing gas, usually air, is
introduced into the bottom of the continuous. reactor in an amount and at a rate
adjusted so as to give substantially complete conversion of the charged toluene to
oxidation products, mainly benzoic acid. Catalyst employed in the reaction is charged
and/or replenished by addition thereof to the continuous recycle loop of benzoic acid
reaction medium. The'mixture of toluene and benzoic acid in the oxidation reactor
contains at least 85%, and preferably over 90 weight percent benzoic acid.

The oxidation of the toluene feedstock is effected in the presence of a heavy metal
oxidation catalyst and advantageously in the presence of a catalyst consisting of a
heavy metal oxidation catalyst and a bromide aifording substance as a promoter. No
novelty is claimed 3,l37,33 Fatented June 1, i905 per se in the catalyst or in the catalyst
promoter employed in this invention since the invention is an improvement in a toluene
oxidation system recently perfected by others. The catalyst is a multivalent or heavy
metal, preferably in a form which is soluble in the reaction medium or solvent. The
catalyst metal may advantageously be selected from the group consisting of
manganese, cobalt, nickel, chromium, vanadium, molybdenum, tungsten, tin, cerium or
mixtures thereof, and the metal may be employed in elemental, combined or ionic form,
preferably as a compound soluble in the reaction medium. The promoter, if used, is a
bromine-affording substance, the bromine being in elemental, ionic or inorganic form.
Thus, the bromine may be employed in the form of potassium bromate, ammonium
bromide, benzyl bromide, tetrabromoethane, manganese bromide or the like. The
proportions of catalyst and promoter may be approximately stoichiometric as
exemplified by manganese bromide and generally are in the range of 1:10 to 10:1
atoms of catalyst metal per atom of bromine. The amount of heavy metal catalyst
employed is usually in the range of about .01 to 10% or more and is preferably in the
range of about .2 to 2% by weight based on the reactor charge. The preferred mixed
metal catalysts are mixtures of manganese in the form of bromide or acetate with
ammonium molybdate, ammonium chromate, tungstic acid, cobalt acetate, or the like,
the proportions usually being about 1 to 2 parts by weight of the manganese salt per
part by weight of the other metal compound. Alternatively, of course, the catalyst metals
may be employed as salts of an acid which is being produced in the system.

The oxidation reaction is effected continuously at an elevated temperature, e.g. in the

range of about 300 450 5., preferably 400-425" F., and elevated pressure, for example
-500 p.s.i.g., preferably about 300 p.s.i.g. The oxidation of toluene under these
conditions is a highly exothermic reaction, and an important aspect of the process is the
conduct of the continuousoxidation PTO? cess under essentially adiabatic conditions.
The temperature ofreaction is controlled by continuous recycle of an externally cooled
recycle stream of benzoic acid, heat removal external to the oxidation reactorbeing
efiected by indirect heat exchange of the recycle benzoic acid with process water. By
this means, process steam is produced which can be employed to effect a substantial
savings in overall economy in plant operation. In operation of the process, the recycle
stream of benzoic acid is cooled to a temperature sufficient to provide a recycle stream
of benzoic acid, together with charged toluene reactant, of about 300-350" F. I

The total product from the oxidation reactor is withdrawn and passed to a flash chamber
or tower operated at 375400 F. and sub-atmospheric pressure. -In a preferred
embodiment of the invention, a major portion of the oxidation reactor efiluent is passed
through a coilor conduit in the dash chamber, a minor portion of thereactor eflluent
being introduced into the flash chamber in indirect heat exchange relation with the
major' body of recycle benzoic acid. Benzoic acid accompanied by small amounts of
connate impurities more volatile than benzoic acid, e.g. benzyl bromide, benzoyl
bromide (where a bro.- mine compound is used as a catalyst component), benzyl
alcohol, benzaldehyde and water is continuously flashed off in the flash chamber to
suitable recovery means hereinaf-ter described for recovery of the benzoic acid
produced. By flashing only a portion of the reactor efiluent, a flash chamber residue is
obtained having a substantially higher concentration of catalyst and associated
impurities, which residue can then be partially discarded as a purge from the reaction
system. Make-up catalyst to contained in the benzoic acid-beingremoved overhead as
vapor. Bottoms from the reflux tower consisting of pure molten benzoic acid are
withdrawn as a product liquid stream and subsequently subjected to further purification,
if desired, or cooled, flaked and bagged as pure product.

Furtherobjects and aspects of the invention will be apparent from the following detailed
description of a specific example thereof read in conjunction with the accompanying
drawing which forms a part of the specification.

This invention will be described as applied to the conversion of about 4000 pounds per
hour of toluene charging stock to about5300 pounds per hour of benzoic acid.

from coil 28 consisting inthis example of about 212, 750' Referring to the drawing,
toluene obtained from storage,

an'increase in temperature in the reactor, and liquid effluent continuously removed from
the upper part of the reactor is at a temperature of about 430 F. Charged toluene is
converted substantially completely to'benzoic acid; minor amounts of water, light
impurities (cg. benzyl alcohol, benzaldehyde, benzyl bromide and the likeland heavy
impurities (e.g. benzyl benzoate, bipheny-l, benzoic anhydride and the like) being
concomitantly formed. Water in an amount of 720 pounds/hour is removed via line 23
with the r-eactor'cxit gases, containing in'this "example 0.5% oxygen and 2.0% carbon
dioxide.

- and introduced directly into flash drumf29.

not'shown, enters through line 10 controlled by valve 11'. and is mixed in line 12 with
recycle benzoic acid entering through line 13 and make-up oxidation catalyst entering
through line 14. The catalyst is preferably a cobalt or manganese salt,'as tor example
the benzoate,roleate, or other carboxylic acid salt of one or both of these metals and
optionally a bromine supplying substance, e.g. am-

monium bromide, tetrabromoethane, etc. 7 The amount of catalyst added via line 14 is
controlled so as to maintain a metal content based on total charge to the oxidizer,
between about 0.01 and 10 weight percent preferably be tween 0.2 to 2%. In this
specific example," manganese ti'on in the reactor is 0.5 weight percent. and the
ammonium bromide content is 0.25 weight percent;

The feed mixture entering through line 12is'passed int-o the oxidizing vessel 15 which
may be a pressure revice 16 operated. by'motor 17. Oxygen, air, or other oxygen-
containing gas is introduced into the oxidation vessel through line 18 controlled by valve
19. In this example, air at a rate of 362 moles/hour provides satisfactory conversion of
substantially all of the toluene charged ,to. oxidation products, mainly benzoic, acid.
Spent gases are vented by line 21 through knock-back condenser 2.2"which is
maintained at a temperature of about 300 F.; water vapor and uncondensibles being
vented via line 23,, while entrained benzoic acid and condensibles are returned via line
24 to the oxidizer. The pressure in the oxidizer is controlled by meansof valve 23a which
permits regulation of the rate of'flow of spent gases and water vapor. Oxygen'introduced
to the reactor is controlled so as to provide a maximum oxygen concentration
inicondenser 22 and vent line 23 of lessthan 8%, preferany below about 2% to avoid
explosion hazards.

Reactor 15 is initially charged with benzoic acid, heated 'to a temperature of about 430
F. and pressured with an j inert'gas, e.-g; nitrogen, to about 300 p.s.ig; Alternatively,

During continuous operation, reactor effluent is, continuously removed via line 25
bymeans of pump 26,

from which the reactor efliuent is divided into two streams, a major portion passing by
line 27 to closed coil 28 located within flash drum 29. A minor portion of the efiluent is
withdrawn via line 31 controlled 'by valve 32 In this example, valve 32 is adjusted to
provide a flow of about 98 volume percent of the reactor effluent through coil 28, the
remainder or about 2% of the reactor charge being passed directly to the flash drum as
shown in the accompanying figure.

Considering the recycle benzoicacid stream first, effluent 12 for recharging to the
reactor. 1,

Invessel 29, whichmay be a conventional flash drum 7 for preferably a flash

towerprovided with several fracacetate and ammonium bromide are employed as
catalysts, in an amount such that the manganese acetate concentrationating trays, the
definedconditions'eifect separation of a benzoicacid-rich vapor stream containing a
minor amount of volatile impurities. Flash tower 29 may be provided, as shown in the
accompanying figure,.with an overhead partial condenser or coil 35 to provide a reflux
ratio of about 1:10 in the tower. In this case, there is maintained ;a1liquid level in flash.
tower 29 at a temperatureof 380 F. and a pressure of about 2.3 p.s.i.a. to provide a
bottoms recycle stream,.removcd from the flash tower 2 9 via line 36, of 1920 pounds
per hour of benzoic acid and about 3.40 pounds of oxidation products other than
benzoic acid. 'About 35% of this bottoms recycle stream is continuously removed by line
37 and pump Y38 and discharged to waste via line 39.' The remainder of the bottoms
recycle stream passes by valved line 41 to r i recycle drum 42 which may be a
conventional holding vesse1, jacketed and heated to maintain the benzoic acid in
toluenemay be charged to the reactor, together'with the 7 requir'edquantity of catalyst,
and the toluene converted to benzoic acid by airoxidation prior to continuous onstream
operation of theoxidation system. During con- ;tinuous operation, reactor'pressure is
maintained at about in this example 315 p.s.i.g., and recycle ban- 7 together with fresh
toluenefeed," are introduced'to the reactor through line 12 300 p.s.i.g., vzoic acid
containing connate impurities,

. at a temperature of 340 Heat of reaction results in i molten condition. Pump 44 is

provided to recyclematerial removed'by line 43 from drum. 42, via line 46 to'lin'e 12 for
return to the oxidation reactor.
Returning now to flash tower'29, the slipstream of reactor effluent introduced via line 31
provides an overhead vapor stream consisting in this example, of 6133 pounds per hour
of benzoic acid togetherwith 184 pounds per hour. of water and about pounds per hour
of volatile impurities. This vapor stream passes by line 51 controlled by valve 52'to hot
condenser 53 and thence by line 54 to refining tower56, Condenser 53' is not essential
to the 0 operation of the described process, but can be employed to efiect
partialcondensation of the vapor stream from flashftoweri29'and thus reduce the number
oftrays re quired in the lower portion of refining tower 56. In' this example, refining tower
56 comprises a conventional. distillation column provided with a reboiler, and is
operated ata bottom temperature of 384 F. under vacuum providedby" steam ejector 70
ata pressure of 2.0-3.0 p.s.i.a. Vapors from the refining tower pass by line 57 at a
temftofoverhead hot condenserSS'Which is operated perature of 260-2S0 F., providing
a reflux stream of benzoic acid and light impurities which is returned by line 59 to reflux
splitter 61. A major portion of the reflux stream is returned by line 62 to the upper part of
the tower 56, while the remainder (about is returned by line 63 controlled by valve 64 to
recycle drum 42. During continuous operation, refining tower 56 is operated at a reflux
ratio of about 10:1, providing an overhead water vapor stream of 184 pounds per hour
removed by line 65, condensed and discharged to waste via condenser 66, drum 67,
and line 68. Molten benzoic acid free of Water and impurities continuously accumulates
at the bottom of tower 56 from which the product is removed via line 69 by pump 71 to
product line 72. Product benzoic acid is obtained at a rate of 5370 pounds per hour, of
high purity suitable for most commercial applications. If desired, the benzoic acid
product can be subjected to additional purification, e.g. to distillation or crystallization
from water or other solvent to provide an extremely pure benzoic acid product.

While .the foregoing example has been described in considerable detail with respect to
various operating conditions for the production of benzoic acid by continuous oxidation
of toluene, it will be understood that various alternative operating techniques, steps and
conditions as will be apparent from the foregoing description to those skilled in the art
may be employed without departing from the scope of the invention as hereinafter
claimed.

I claim:

1. A continuous process for the production of benzoic acid from toluene, which
comprises in combination the steps of introducing into a liquid phase of benzoic acid
having heavy metal oxidation catalyst dissolved therein in an oxidation zone liquid
charging stock comprising essentially at least 85 weight percent benzoic acid and a
finite amount, up to about 5 Weight percent, of toluene, contacting said charging stock
in the presence of heavy metal oxidation catalyst dissolved in said charging stock with
molecular oxygen introduced into the bottom of said liquid phase in said oxidation zone
in an amount suflicient to effect substantially complete oxidation of toluene in said zone,
operating said zone under essentially adiabatic conditions at pressures in the range of
about 100 to about 500 p.s.i.g. and temperatures in the range of 300 to 450 F
continuously withdrawing from said oxidation zone liquid efliuent essentially free of
toluene, separating at the pressure range in said zone said effluent into a liquid recycle
stream and a liquid minor stream, said recycle stream being greater in weight than said
minor stream, introducing said minor stream into a flashing zone operated at
subatmospheric pressure and at 375 to 400 F, contacting within said flashing zone said
minor stream in indirect heat exchange relationship with said recycle stream
simultaneously thereby effecting partial cooling thereof and vaporizing a portion of said
minor stream, thereafter further cooling said recycle stream to a temperature in the
range of from 300 to 350 F., pumping a portion of the cooled recycle stream into said
oxidation zone, removing from said flashing zone a benzoic acid rich portion said minor
stream also having materials more volatile than benzoic acid and leaving a liquid
bottoms stream and heavy metal oxidation catalyst dissolved therein together with
materials less volatile than benzoic acid, pumping said liquid bottoms stream into said
oxidation zone, charging said benzoic acid rich portion removed as vapors from said
flashing zone to a distillation zone operated at 1.5 to 5.0 p.s.i.a. and a bottoms
temperature of 350 to 400 F. to provide as an overhead frac- 6 tion the materials more
volatile than benzoic acid and liquid product benzoic acid as a distillation bottoms
fraction, and continuously recovering the liquid product benzoic acid distillation bottoms
fraction.

'2. In a continuous process for the production of benzoic acid from toluene wherein a
charging stock consisting essentially of at least weight percent benzoic acid and a finite
amount, up to about 5 weight percent, of toluene is oxidized in the presence of heavy
metal oxidation catalyst with molecular oxygen at a pressure in the range of from about
to about 500 p.sig. and a temperature in the range of from about 300 to 450 F. under
essentially adiabatic conditions in an oxidation zone and wherein liquid efiluent
essentially free of toluene is continuously withdrawn at the pressure in said oxidation
zone from said oxidation zone, the improvement of separating said eflluent at said
pressure into a liquid recycle stream and a liquid minor stream, said recycle stream
being greater in weight than said minor stream, introducing said minor stream into a
flashing zone operated at suba-tmospheric pressure and at a temperature of 375 to 400
F. and contacting said minor stream in said flashing zone in indirect heat exchange with
said recycle stream whereby simultaneously a benzoic acid rich vapor mixture also
having materials more volatile than benzoic acid is formed and said recycle stream is
partially cooled, thereafter further cooling said recycle stream to a temperature in the
range of 300 to 350 F. by the generation of steam from water and pumping a portion of
the cooled recycle stream into said oxidation zone, removing said benzoic acid rich
vapor mixture from said flashing zone leaving a liquid bottoms stream having dissolved
therein a portion of the heavy metal oxidation catalyst and material less volatile than
benzoic acid and charging said benzoic acid rich materials into a distillation zone
operated at 1.5 to 5.0 p.s.i.a. and 350 to 400 'F. to provide an overhead fraction
consisting of materials more volatile than benzoic acid and a liquid product benzoic acid
bottoms fraction which is continuously withdrawn from the distillation zone.

1.A continuous process for the production of benzoic acid from toluene, which
comprises in combination the steps of introducing into a liquid phase of benzoic acid
having heavy metal oxidation catalyst dissolved therein in an oxidation zone liquid
charging stock comprising essentially at least 85 weight percent benzoic acid and a
finite amount, up to about 5 weight percent, of toluene, contacting said charging stock in
the presence of heavy metal oxidation catalyst dissolved in said charging stock with
molecular oxygen introduced into the bottom of said liquid phase in said oxidation zone
in an amount sufficient to effect substantially complete oxidation of toluene in said
zone,operating said zone under essentially adiabatic conditions at pressures in the
range of about 100 to about 500 p.s.i.g. and temperatures in the range of 300* to 450*f.,
continuously withdrawing from said oxidation zone liquid effluent essentialaly free of
toluene, separating at the pressure range in said zone said effluent into a liquid recycle
stream and a liquid monor stream, said recycle stream being greater in weight than said
minor stream, introducing said minor stream into a flashing zone operated at
subatmospheric pressure and at 375 to 400* f., contacting within said flashing zone said
minor stream in indirect heat exchange relationship with said recycle stream
simultaneously thereby effecting partial cooling thereof and vaporizing a portion of said
minor stream, thereafter further cooling said recycle stream to a temperature in the
range of from 300 to 350f., pumping a portion of the cooled recycle stream into said
oxidation zone, removing from said flashing zone a benzoic acid rich portion said minor
stream also havig materials more volatile than benzoic acid and leaving a liquid bottoms
stream and heavy metal oxidation catalyst dissolved therein together with materials less
volatile than benzoic acid, pumping said liquid bottoms stream into said oxidation zone,
charging said benzoic acid rich portion removed as vapors from said flashing zone to a
distillation zone operated at 1.5 to 5.0 p.s.i.a. and a bottoms temperature of 350 to
400*f. To provide as an overhead fraction the materials more volatile than benzoic acid
and liquid product benzoic acid as a distillation bottoms fraction, and continuously
recovering the liquid product benzoic acid distillation bottoms fraction. Metal oxidation
catalyst dissolved in said charging stock with molecular oxygen introduced into the
bottom of said liquid phase in said oxidation zone in an amount sufficient to effect
substantially complete oxidation of toluene in said zone, operating said zone under
essentially adiabatic conditions at pressures in the range of about 100 to about 500
p.s.i.g. and temperatures in the range of 300* to 450*f., continuously withdrawing from
said oxidation zone liquid effluent essentially free of toluene, separating at the pressure
range in said zone said effluent into a liquid recycle stream and a liquid minor stream,
said recycle stream being greater in weight than said minor stream, introducing said
minor stream into a flashing zone operated at subatmospheric pressure and at 375 to
400* f., contacting within said flashing zone said minor stream in indirect heat exchange
relationship with said recycle stream simultaneously thereby effecting partial cooling
thereof and vaporizing a portion of said minor stream, thereafter further cooling said
recycle stream to a temperature in the range of from 300 to 350*f., pumping a portion of
the cooled recycle stream into said oxidation zone, removing from said flashing zone a
benzoic acid rich portion said minor stream also having materials more volatile than
benzoic acid and leaving a liquid bottoms stream and heavy material oxidation catalyst
dissolved therein together with materials less volatile than benzoic acid, pumping said
liquid bottoms stream into said oxidation zone, charging said benzoic acid rich portion
removed as vapors from said flashing zone to a distillation zone operated at 1.5 to 5.0
p.s.i.a. and a bottoms temperature of 350 to 400*f. To provide as an overhead fraction
the materials more volatile than benzoic acid and liquid product benzoic acid as a
distillation bottoms temtion, and continuously recovering the liquid product benzoic acid
distillation bottoms fraction.