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. Patented Jan. 25, 1938
Q j ‘ 1,106,521,
- - UNlTED'STA'l'lIS PATENT oFFicaF
‘
2,106,521
'
'
p
-
_
"commons mn'rnon or REAGTING
‘mourn REAGENTS
.—
Richard lid. Deaneoly, Berkeley. Calif” assignor
to Shell Development Company, San Francisco,
Calif., a corporation of Delaware
.'No Drawing.. Application September 9, 1935,
Serial No. 39,809
‘
1s ouma. (c1. zoo-99.12)
This invention deals with a novel procedure for
conducting chemical reactions between liquid re
actants, particularly liquid reactants, each of
which has a low physical solubility in the other,
.5 in a continuous manner whereby greater e?lciency,
‘ in the consumption of reagents and economies of
the reaction substantially takes place ‘whereby
eiiicient use may be made of all reactants and
highreaction rates attained. ~
.
.
-
‘Y
My invention may be practicedtwith any suit- I
able reactants in the liquid state which form re
action mixtures made up‘o two liquid phases,
operation may be e?ected.
regardless of the nature of t e chemical reaction
- The process of my invention essentially com
or reactions involved. As examples of the diverse
prises continuously adding the liquid reactants to
_10 a reaction mixture of a composition with .respect
reactions to which my invention may be applied,
the nitration of toluene, the sulfonation of ben 10
to elements in the feed which differs from the
zene, the hydrolysis of amyl chloride, the saponi?- ,
composition of the total feed with respect to those
cation of esters, particularly fats and fatty oils,
elements. To this end I ?nd it advantageous to and the esteri?cation, etheri?cation and ~hydra- "'
continuously return to the reaction zone a sub ‘ tion of oleiines may; be mentioned as typical.
15 stantial part of one constituent of the reaction, While my invention is thus broadly applicable
whether a reactant or a reaction product thereof, ' wherever liquid reagents of low physical solubility '
‘ preferably after separation therefrom of any with respect to each other are reacted to give re
. diluent materials which may be present-therein, action ‘mixtures made up of two liquid, phases, it
. 'while withdrawing a reaction product from the has particular advantage in the treatmentv of hy
20 system substantially ‘at the rate at which'it is drocarbons with aqueous reagents since the solu-.
formed. By this procedure I have found it pos
bility relationships are especially adverse in such
sible to adjust the conditions of reaction to the reactions. For this’reason my invention will be
properties, both chemical and physical,’ of the re
‘ _
described with more particular reference to re
actants so that each of the components may be - actions of this class, especially the typical case
25 provided with a time of residence in the reaction ' of the production of ole?ne derivatives by absorp
zone best suited to its properties independently tion of the corresponding ,ole?ne in acid acting
of the other component or components.
media, but it will be understood that this is merely
My process is thus radically different from prior in the interest of‘ conciseness and clarityiand‘ ~
Procedures for reacting together reagents one of ' impliesnov limitation since by obvious modi?ca
'30 which has a low physical solubility ‘in the other,
‘since such prior methods have been largely re
stricted to batch operations with their obvious at
. tendant disadvantages prominent among which
are usually an undesirably long. induction period
which materially reduces theaverage production
rate of the apparatus and high labor costs, etc.
tion my invention may be applied with equal .ad 30
vantage not only to the other types of reaction’
listed above but also to many other reactions
“between still different liquid reactants.
As applied to the manufacture‘ of ‘alcohols,
. Proposals have" been madeJor carrying out such
ethers, esters and'li'ke derivatives which maybe
producedby absorption of the corresponding ole
?nes in acid acting-media, my invention may be
reactions continuously-whereby some of. the de?
practiced wtih any suitable ole?n'e or ole?nic
mixture regardless oithe source or character of
4_0 The continuous methods proposed heretofore‘ suf
its olefine content. As suitable starting material,
fer from the disadvantage of not providing for hydrocarbons derived from mineral oils aspetro
"prompt removal from the reaction. mixture of leum, shale oil, and the-like, or from mineral oil
components thereof which are undissolved in .the - products, orIfrom-natural' gas, or from c'oaL-peat \
phase in which reaction takes place. This loads and like carboniferous natural material, 'may be
45 to undesirable dilution of the reaction mixture used,’ as well as those derived vfrom animal-and
‘ .' and greatly reduced capacity of apparatus. ' My vegetable oils. fats and waxes. The ole?nes pres
method. on the other hand not only provideafor ent in such starting_mat'erial may. be‘ of natural
_'__"“the continuous‘ removal. of such components of occurrence,’ the result ot- dehydrogenation, distil
the reaction’mixture butalso permits selective lation, vapor or liquid phase cracking, or other
- ciencies of the batch methods maybe overcome.‘
59 return to the reaction zone of the phase in which
1
pyrogenetic treatment._ The oleiines may be used 50
21
2, 106,581
in a pure state, either as individual ole?nes or
pure ole?nic mixtures, or in admixture with .
para?ins .or other compounds which may. be,
considered as inert in the process. Furthermore;
such ole?nes may comprise hydrocarbon fractions 1
‘ If'we consider the case of the reaction between
two liquids. or components oifv them of limited
physical solubility, it is clear that the complete ‘
reaction .requires two steps which may be con
sidered separately, viz. ‘ I-the transfer by agi- ‘
consisting of, or predominating in, hydrocarbons‘; tation of the reactant in one‘ phase to a state of
containing the same number of carbon atoms to 1 solution in other phase-the- latter being the
the molecule, or of mixtures of non-isomeric hy- - phase in which predominantly, if not wholly, re
drocarbons. Ethylene and/or secondary‘base ole
action takes place, and II.—the homogeneous
Ii) ?nes (i. e. ole?nes, both iso and normal, which
yield secondary derivatives, as propylene,>1-bu
tene, 2-butene, l-pentene, Z-pentene, 3-methyl
l-butene, and the like) and/or tertiary-base
ole?nes (i. e. iso-ole?nes which yield tertiary dc‘
15
rivatives, as 2-methyl propene, 2-methyl-2-bu
tene, 2-methyl-1-butene, and higher homologues
chemical reaction in the latter phase. For most 10
e?lcient utilization of the reaction zone, 1. e.'
greatest overall reaction rate, it is desirable that '
there shall be present in the‘ reaction zone the
greatest possible ‘amount of the latter phase, sub
ject to the provision that there shall be as much
of the former phase as is required to permit a
rate of transfer of. reactant by agitation from the
former phase to solution in the latter equal-to the
in this application of my process include: ins ' rate of reaction of the transferred reactant in the
20 organic acids, of which sulfuric, phosphoric, pyro
latter (or reaction) phase. Now while the condi
phosphoric and hydrochloric are typical; or or-' ' tions conducive to. the physical process of rapid 20
ganic acids, as‘ benzene sulfonic, naphthalene phase transfer are those of degree of turbulence,
sulfonic, toluene sulfonic,'and homologues and interfacial tension and the like, the conditions
analogues thereof; or "acid liquors” such as are conducive to the chemical process of homogeneous
and analogues) may thus be used.
Suitable acid acting media which may be used
obtained _by the absorption of ole?nes in mineral
acid acting acids such as the above; or aqueous
solutions or suspensions of acid-acting salts, such,
for example, as sodium bisulf-ate, and the like.
The concentrations in which such acid acting
'30 media may be used'in any particular case will de
pend upon the nature of the acid acting compound
and ole?ne or ole?nes employed, the concentra
tion of the plefine or ole?nes used and the tem
perature at which the absorption is carried out.
36 When the acid acting agent is sulfuric acid, for
exampl‘e, I have found'that concentrations with;
in the range of about 40% to about l00.% may be
satisfactorily used. For the absorption of ter
tiary-base ole?ne concentrations of about 40%.
40 to about 80% are preferable, while for secondary
.base ole?ne concentrations of about 80% to about
100% are more suitable. Irrespective of the tem
perature conditions or acid concentrations used
Iprefer to ‘carry out the process with the ole?ne
45 or ole?nes undergoing. treatment in the liquid
phase, that is, at ‘pressures greater than the vapor
_ reaction are temperature and concentration of 25
reactants and catalysts. It is the purpose of this
' invention to achieve an arrangement of operat
ing conditions which satisfy these independent
requirements and is not limited by the stoichio
metric relationships of the reaction which govern so,
the composition of the feed.
Whereas in the prior art in continuously react- '
_ ing together liquid reagents in a mixing zone and
continuously withdrawing reaction products in
equivalent amount, proportions of the chemical 35
elements present inrthe reaction zone were in
variably those proportions present in the feed, .
with the novel arrangement here described the
proportions in the reaction zone can be varied
entirely ‘independently of the proportions in the 40.
feed with , resultant considerable advantages.
Whereas formerly if it was desirable to carry out a
reaction continuously‘in thepresence of a large
excess of one of the components of the reaction
whether reactant or product, it was necessary to
add that excess of component to the .feed and
pressure of the ole?ne at the operating tem'pera- V remove it from the product in a separate opera;
tures. By operating with the ole?ne in_ the liquid tion process, with the presentarrangement-that '‘
phase, more accurate control of the proportions desirable excess of one component in the reaction
50 of acid phase to hydrocarbon in the reactor may
be had in a very simple manner irrespective of
the proportions of the feed or products.
a
mixture can be achieved while introducing the 60
reactants as feed in the stoichiometric propor
tions;
_
-
In general reactions between liquidsreagcnts of‘
low physical solubility with respect to each other
In‘ .the absorption of ole?nes in acid acting
media,
the rate of transfer of ole?ne from hydro
55 appear to take place predominantly in one of the
‘carbon phase to acid phase depends not only on
phases -only,~thus I have found that the reaction the degree of agitation,‘ altho this is highly im
of ole?nes with acid acting media takes place in
the acid phase, so that, provided enough agitation
is created to maintain the acid phase saturated
vwith ole?ne, the output of a reactor, other things
beingequal, depends upon .the volume of acid
portant, but also upon the inter-facial tension
and, diifusioh and solubility characteristics of .
the ole?ne'wlth respect to the acid phase, which
vary m‘arkedly with the composition of the acid
phase. The velocity of the homogeneous reaction '
phase present. The volume of acid phase which in the acid phase is in?uenced to an even greater _' '
,; may be present is only limited’by the size of the extent by~thesolubility of the ole?ne in the com ‘
mixing unit-which in any given case will be deter
phase, the rate of reaction increasing as the con
mined by economic considerations of pump and centration of adsorbed but lmreacted ole?ne in 65 .
creases. Depending upon the ole?ne or ole?nes . '
separator size. ' The latter in particular, is pref
erably limited to such a size as will make excessive being treated, the composition of the acid layer
recycled in accordance with my invention will
residence times whether in the separator or‘re
vary. In the case of the tertiary base-ole?nes
actor,“
which
might
lead
to
decomposition,
un
70
necessary. .The minimum size reactor, on the where‘
to the corresponding
absorption in aqueous
tertiary acid
alcohol
andare, for all 70
other hand, is that which when maintained prac ,practical purposes, synonymous. the acid layer
tically full at all times permits the transfer under will have an alcohol content practically eqmw
agitation of as much ole?ne per imit- time as-will lent to the reacted ole?ne content, while for
.
'
16 react with the acid phase.
abmrption products of
and similar
2,100,521
.
_
.
-
3
ole?nes which form less easily hydrolizable ad
about two minutes. The following'results were
dition products with the mineral acid acting
acid present, the acidic layer will have a com‘;
obtained:
>
1
’
'~
"‘
'
isobutylene content of the‘; dis
position characterized by'ratios of esters to free I Unreacted
charged hydrocarbon layer
' _
alcohol determined by the hydrolysis equilibrium
per cent by volume__ 10.5
of those esters under the reaction conditions} '
Due to the low free water content eof the re-l Absorbed isobutylene in the absorption prod
uct as % of the isobutylene fed to the
cycled acid, the decline in activity of the acid
reactor _.._'_____'_ _____ __ ____ _‘_per cent... ‘72.7’
owing to dilution with reaction products‘ is more
Mols of isobutylene absorbed per‘ mol. of
10 than offset, up to a certain point, by the in
sulfuric acid used.‘ _______ __'___-_mols__ 1.64
creased solubility of unreacted ole?ne .in the
acid phase. Thus the overall rate of reaction - Gallons of tertiary'butyl alcohol produced‘
per 24 hours per gallon of reaction
,is not by any means lowered as a result of re
gallons“ 38.2.
cycling acid layer, and so, in effect, reacting the
l5 ole?ne with nearly fully reacted acid.
Further, In larger scale operations it has been found 15'
' the use of nearly fully reacted acid of low total ' more advantageous to replace the ‘above de
acidity as the absorption medium permits. the scribed mixer by an'ei’?cient centrifugal pump
10;
Spa"
’
.
'
employment of temperatures very much higher
and a series of tubes having a volume equivalent -
than would be safe with fresh acid
to that of a mixer of the required increased ca
The actual conditions of operation adopted in
pacity.. In this system it is particularly desir
20 v
any given case will depend upon the eillciency of ' able to ‘provide a .by-pass whereby the emulsi
conversion desired. It has been found for ex
?ed reactants may be recirculated and unneces
ample, that isobutylene present in a concentra- . sary load on the separator thereby avoided.'
'
tion of 20%v in 80% of inert diluents may be con
In Example I there was available a hydro
verted to tertiary butyl alcohol-by my method at
a'rate of about 25 to 30 gallons of anhydrous
carbon mixture'which it was desired. in order to 25
comply with the stoichiometric requirements of
alcohol per dayper gallon of reaction space with ' the reaction,-to react continuously with one
a conversion of over 85% of the isobutylene in
the feed. Much higher rates of thruput are
30
possiblewhen the conversion is allowed to fall.
fifth of its volume of sulphuric acid of a cer
tain strength. By the methods previously used
the passing of this feed at a rate of ?ve gallons
The following examples which show applica
so
of hydrocarbon per-hour continuously through a
tions of my invention to the selective absorption mixing and reaction zone of 1 gallon volume
of tertiary and secondary base butylenes in would have resulted in there being present in
aqueous sulfuric acid, illustrate 'the advantages they reaction zone at all times ?ve-sixths of a
of my'novel process.‘ It will be understood, how gallon of hydrocarbon to one-sixth of a gallon 35
ever, that as has already been pointed out, many‘
of acid (ignoring volume changes due to reac
other applications and modi?cations are possible > tion) so that both materials would have a resi- . '
dence time in the reaction zone of one-sixth of
an hour. Now thisv residence time of'one-sixth
of an hour is more than su?icient for the physi 40'
without. departing from‘the spirit of my inven
tion.
‘
~
Example I
cal processor phase transfer of the'whole of the
As starting material for theproduction of ter
reagent from the hydrocarbon phase into the
tiary butyl alcohol in one typical instance, a' acid phase, but is less than su?lcient to permit
butane-butylene fraction ‘having the following the chemical reaction of this quantity of reagent
approximate composition was used.
'
1 Per cent by volume
Paraffin hydrocarbons___*_ ______________ __ 30.8
. Butene 1 and butane‘ 2 _____________ _>____ 29.6
Isobutylene
‘
39.6
'50
‘This hydrocarbon mixture was fed, in the liquid
state, at a rate of about 3.13 gallons per hour
per gallon‘ of reaction space to a' continuous re
actor comprising a mixer of about 800 cc. vol
ume ?tted with a high speed stirrer so as to act
as an ine?lcient centrifugal pump and discharge
from the circumference to a separator. At the
in the volume of acid phase present.
-
- 45
Accordingly by the methods of my invention I
reduce the residence time of the hydrocarbon
phase and increase that of the acid phase by
withdrawing from‘ the reaction zone at a. rate of
‘thirty gallons per hour to a separator and return 50
from the separator to the reaction zone twenty- .
four gallons per hour of the acid phase. Thus
altogether Ihave entering and leaving the re
action 5 gallons per hour of hydrocarbon and 25’.
gallons per hour of, acid made up of one gallon 'of
fresh acid and twenty-four gallons of recycled _
acid phase, 1. e. acid'which contains absorbed
' same 5time a 63.2% solution of sulfuric acid
ole?ne, so’ thatthe reaction zone now contains
ma'tely 49° C. and the‘ rate of ‘discharge there
from was kept substantially constant at about
30 gallons per hour per gallon of reaction space.
.*"The reactor and separator were maintained
under ‘sufficient pressure (e; g. about 100 to 150
acid phase'of all they-reactant hydrocarbomwhile "
the’ acid phase is inemulsi?ed contact with the .
one-sixth of a_ gallon of :hydrocarbon- and ?ve
was added at the rate of about one gallon to sixths of a gallon of acid phase. Thus the hydro GO
each 5 gallons of hydrocarbon feed. The tem carbon now has a residence time of one-thirtieth
‘perature of the‘ reactor was kept at approxi- ‘ ‘of an hour, which suf?ces for the physical, process
lbs./_sq. in.) to ensure both being kept full at
alltimes and the unabsorbed hydrocarbons were
withdrawn as fast as separated whilea part of
" the absorption product was. recycled‘ to give a
ratio of about -11 volumes of acid phase to one
volume of hydrocarbon phase 'in-the reactor and
75 an average time of contact of the two phases ofv
of transfer from the hydrocarbon phase to the
hydrocarbon phase for ?ve-sixths’ of an hour.»'
The acid‘ phase now has a ?ve times greater
volume inthe reaction-zone than in the former‘
case and the amount of reaction which can there 70
fore take place in it is vincreased proportionately.
The extra‘degree of freedom'in choice'of operat- -
ing conditions and consequentrarivvantage ?ll/11S
obtained enabling the" adjustment cf conditions
.to the requirements of thexprocess‘is thus clearly.
4
‘2,108,521
seen whether from the standpoint of adjusted
possible. For example, results practically identi
residence time or adjusted reaction phase volume.
Example H
cal to those described in the above examples may
be obtained by substituting phosphoric acid solu—
tions of the same concentrations for the sulfuric
acid solutions described. Another modi?cation 5
which may sometimes be desirable, a'ltho involv
ing more equipment, comprises carrying out the
' In order to compare the e?ect of recycling
hydrocarbon layer instead of acid layer the fol
lowing tests were made using the same apparatus.
In each case the isobutylene content of the
absorption in more than one step.
10 the sulfuric acid was 64%.
Recycling hydro
' layer
15
on the same oieiine containing material may be 10
,
Recycling acid
carbon layer
M015 0! a??? _Mols oi ‘Lea-cs?‘
isobuty‘ butylene lsobuty' butylene
leue
-.
led
lsobutylene input- _-_. --
79. 8
100. 0
Isobutylene in acid layer.
20 Isobutylene
in hydro-
' 65. 0
82. 5
butyl alcohol ________ --
lene.
_ fed
.
54. 3
100. 0
an “acid liquor?’ as absorption medium for one
61. 5
stage of the operations and approaches in eifect
v
I
.
2.4
3. 0
2. 2
7. 75
9. 5
12. 8
'
ed for ________________ .-
Duration of experiment_Average tertiary butyl
4.0
5 0
alcohol content of acid
layer__ ___________ _>.____
7.7 hours
6.0
the mineral acid acting acid agent. The use of
alkyl acid esters of mineral acid acting acids as
11.1
absorption agents is especially useful where both
3. 9
6.0 hours
A
"
45.1% i
25.2%
A
4
Average production rate
(gram mols of total al
cohol per hour) ______ __
.30
8.8
the use of an alkyl acid sulfate, for example, as
23. 3
'
lsobutylene unaccount
25
used, a major portion of the resulting-absorption
product being recycled to the same mixer in each
case and'the separated portions of the absorption
products being combined for working up into the
desired end product, or the minor part of the
absorption product from one stage may be used
in lieu of fresh acid in -a preceding stage. The‘
latter procedure is the equivalent of the use of
33. 4
'
carbon layeras tertiary
As free .isobutylene- _ _._.
Thus two or
more independent mixers operating successively
hydrocarbon feed was 40.2% and the strength of
5.9
secondary and tertiary-base ole?nes, particularly‘ 25
_ isomeric secondary and tertiary-base ole?nes, are
to be absorbed. In such cases the secondary-base
cle?ne or ole?nes may be absorbed in a polybasic
mineral acid acting acid of appropriate strength
and that partof the resulting absorption product
30
These results show the advantages both in in- creased rate of production and emciency of op-_ which is separated from the recycled portion may
eration obtainable by having a large volume of be used, advantageously after dilution, to absorb
desired tertiary-base ole?ne using my novel
recycled acid layer present during absorption. the
recycling step as before. In this way substantial
In the above case about 95 to 97% of the contents acid economies may be effected since the total
of the reactor was acid phase when acid layer was‘ ole?ne content of the ?nal absorption product 35
recycled and only about ‘10 to 15% when the acid - may be much higher than is commercially feasible ,
passed thru only once.
.
in prior art procedures. Whatever modi?cation "
v
‘ Example‘ III
e
of my process is used,git'is desirable to separate
40
For the preparation of an absorption product unabsorbed hydrocarbons from the recycled acid 40
> of secondary-base butylenes in sulfuric acid, a
liquid hydrocarbon mixture obtained as a hydro
liquor as needless dilution of the-reaction mixture
is thereby avoided.
Altho the above examples have been described
carbon layerv from a butane-butylene fraction
‘which had been treated according to the pro
45 cedure described in Example I, was used. This
of alcohols it will be apparent that the absorp
had the following approximate'composition:
be converted, by known methods, into a wide va
with more particular relation to the preparation
45
tion products ob ained by my novel process may
riety of other end products. Distillation of the
absorption product under more acid conditions
than those used for the recovery of alcohols favors
50 l-butene and 2-butene ________________ _
Iso and normal butanes ________________ __
the formation of ethers, while reaction with fatty
This hydrocarbon mixture was fed, together with acids, for example,‘acetic acid, may be used to
84.4% sulfuric acid in the proportion of 1.3 to‘ 1.4 produce the corresponding esters. Alternative
mols of acid per mol. secondary-base ole?ne, to ' ly the alkyl acid sulfates present in the absorp
the above described reactor. The hydrocarbon tion products may be converted by treatment with
feed was at the rate of 6.5 gram molsof second-' alkaline agents such as sodium hydroxide and the
like into salts which are valuable wetting agents
ary-base butylenes per hour and the reactor con
and detergents. Or the absorbed ole?nes may be
" tents were maintained at about 30° C. About. polymerized by rapid heating, preferably underv ~
95% of the acid layer was recycled to the reactor pressure; to give higher boiling hydrocarbons of 60
60
-
Percent
Isobutylene
as before- The average ole?ne content of- the
exit hydrocarbon layer was 6.6%. Only a; very
small amount of polymer about equivalent to the
, isobutylene content of the feed could be detected.
_
high anti-knock value. Alkyl substituted phenols
may be produced by reacting the absorption prod
ucts obtained in my process’ with an excess of
The average composition of the separated acid ‘ phenol. My invention is also useful in the prepa
ration _of pure ole?nes from 'ole?nic mixtures 05
layer wasI '
'
-
_
I I
_
Percent by weight
Secondary butylenes ( 'as alcohol) _______ __ 31.0
Total acid (as H2804) ____ .._' ____ _;__; ____ _._ 59.6
Free titratable acid (as H2804) __________ -_ 49.0
- This represents a 93.4% conversion of .l-butene
since by means of. my novel absorption process the
more reactive of such ole?nes may be selectively
removed and the resulting absorption product
used to regenerate, in a substantially pure form, ,
the absorbed ole?ne by controlled heating.
or
- The foregoing examples illustrate applications’
and 2-butene at a rate equivalent to 16.9 gallons ' of my'invention in which the presence of a reac
' of anhydrous secondary butyl alcohol per day per
gallon of reaction space.
75
’
Many ‘variations in myprocess
are obviously
tion product in the recycled phase increases the
solubility of the other reactant therein'and con
sequently promotes-the homogeneous reaction in
75
s
2,100,591
the recycled phase in accordance with the Mass
action law. The following example which is typif
cal of applications of my invention where an ex
cess of a reactant in the recycled phase accom-.
-
plishes the same result, shows the wide applica-' ’
bility of my process wherever the reaction mix
ture forms two liquid phases.
'
zene sulphonic acid and 9.6% unreacted H2894 ’
and the balance water equivalent to that formed
by the reaction.v The reaction mixture when
under‘ steady operating conditions showed" one
part of upper layer to 12 of lower layer, in contrast
to the (approximately) 2 volumes of upper layer
to 1. volume of lower layer in the feed.
.'
It will be obvious that this continuous sulfona-~
Eicample I V
tion procedure may be applied not only to a wide
Alcohols may be reacted with ole?nes by my . variety of other aromatic compounds including
process to give particularly good yields of. ethers at for example toluene, xylene, nitro benzene and , 10 ‘
high‘ rates. In one such application of my inven
tion a continuous reactor similar to that described
in Example I, was charged with a mixture of
15 methyl alcohol and sulfuric acid in the propor
tion of 3 volumes of alcohol to 1 volume of ‘acid.
A, mixture of 'pentanes and amylenes analyzing
about 25% tertiary base ole?nes was then fed in
together with methyl alcohol in the ratio of 1
other suitable benzene substitution products as "
well as naphthalenes, naphthols, anthraquinone
and the like, but also ole?nes such as ethylene
and its homologues and, by the use of oleum, par
amn hydrocarbons such for example as hexane,
the octanes, etc.
is
,From these typical examples it will be evident _ >
not only that my invention may be used in the
volume of alcohol to 20 volumes of hydrocarbon; production of a wide variety of valuable products
The reactor was maintained at about 50° C. and but also that in all'its many applications it of 20,
- under 50 pounds pressure to ‘prevent volatiliza
fers important advantages over prior methods‘
tion of hydrocarbons. The addition of reactants _of operation. It furnishes a particularly desir- '
was at a rate of about 1 volume per minute per able method for carrying out continuous reac-.
47.4 volumes of reactor contents and the with
tions in which all components of the reaction 25
drawal of emulsi?ed mixture was exactly equiva
mixture including the reaction product are ad
lent. The withdrawn'mixture was conducted to vantageously maintained in the liquid phase in‘
a separator where it was allowed to stratify. All order to avoid undesirable side reactions orv for
the acid layer was continuously returned to the other reasons. It will be evident that while‘ my
reactor while the upper hydrocarbon layer was invention has been illustrated by examples in' 80
removed. After equilibrium conditions had been ' which the operations of mixing and reacting were
reached the upper layer was found to contain on carried out in different apparatus from that used
the average about 18% by weight of methyl for stratifying and separating the phases of the‘
tertiary amyl ether which could be recovered by resulting reaction mixture, such operations may
washing to remove traces of acid and amyl al
readily be .carried out in the same unit by suit. as,
cohol and then distilling. '
\ably providing reaction and separation zones
This method of continuous etheri?cation may therein. ~By my process the. usual induction pe
not only be successfully applied to the higher riod accompanying reactions ‘in‘which ‘the ve
homologues of methyl alcohol, such for example, locity of solution of one reactant in the other’ is
as ethyl, propyl, isopropyl, normal, iso-, second
greater than the velocity of reaction between said 40
ary and/or tertiary butyl alcohols and their suit
reactants, .is substantially avoided and the. re
able substitution products but also to polyhydric suiting‘ average rate of reaction is thereby not
alcohols, such as ethylene, propylene, butylene only increased but also made more uniform,
and like glycols, polyglycols as diethylene glycol, Furthermore my invention has unique advan
dipropylene glycol, propylene-ethylene glycol, etc.', tages in carrying out reactions in the presence of 45
glycerol, sorbitol, etc. In all cases other ole?nes inert diluent materials, particularly where such
besides the tertiary amylenes above illustrated diluent material is immiscible with‘ the reactant
may be used.
phase in which the reaction takes place, since by
This reaction_exempli?es, particularly well, the recycling that phase only from a separator as
advantages of my process using a high proportion described in Examples'I, II and III, not only is
of acid phase to hydrocarbon phase. In this case, undesirable dilution of the incoming reactants 50'
' where the usual batch methods, in which the ratio
of hydrocarbonto acid is reversed, are applied,
about two hours are required to reach chemical
equilibrium despite the‘ best of mixing; .while in
my proceduredless than two minutes are neces
sary under otherwise similar conditions.
"
Example V
For the preparation of benzene sulphonic acid
it is required toreact together benzene and 100%
sulphuric acid in the proportions~ 78 gms.-(89 cc.
_ I approx.) to 98 gms. (53 cc. approx.) .
The react
\ants in these proportions were fed into a reactor
avoided, but also alreaction mixture is provided
which is richer in that phase than can-be ob
tained by. mixing the required amounts of the
two reagents without such selective recycling. ' _
56
While I have in the foregoing described in some
detail the preferred embodiments of my inven
tion and have particularly emphasized its appli-'
cations to reactions of acid acting media with
liquid hydrocarbons'it will be obvious‘ to those 60
skilled in the art that alkaline reagents, as in
the hydrolysis of halogenated hydrocarbons with
NaQH, NazCOa, and the like solutions, for ex;
ample, may also be used. and therefore my in- ‘ \
of 400 cc. volume continuously. Reaction mixture , 'vention is to' be regarded as limited ‘only byv the,
was withdrawn to-a separator at rate of 10,000 terms of the accompanying claims.
cc./hr. or 25 volumes per volume of reactor per
hour. 8000 cc. of the lower layerv from the separa
tor was returned continuously to the reactor and
7‘ the reni'ainder withdrawn as product. The level
in the reactor was maintained by feed of reagents
in the ‘stoichiometric proportions above. The
‘ - produce was found to consist of 9.0% mol. unre- .
acted benzene which separated as upper layer and
'75 could be returned to the process, 89.4% incl, beny'
I claim as my invention:
‘
I
1. .A pro ess for continuously reacting an ‘or
ganic liqui “reagent reactive with another liquid
reagent in which it’ha‘sa low physical solubility
which comprises continuously adding said re
agents to a reaction mixture of a composition
with respect tothe elements in the_.feed which
is'Ydifferent from the composition of the total
iced, continuously removing ‘reaction mixture 75
6
2,100,021
pounds of din‘erent reactivity toward a liquid re
from the‘ reaction zone without substantially
changing its composition, separating at least a
part‘ of the reaction product corresponding to
‘agent in which said component has a limited ,
physical solubility which comprises continuously
contacting saidhmixture in the liquid state with
that formed in the reaction and continuously re
said liquid reagent at a temperature and at a
pressure at which reaction between the more re-‘
turning sumcient of a remaining component of
the reaction mixture to said reaction zone .to
active component and the liquid reagent takes
place in the presence of substantially reacted
liquid reagent without substantial conversion of
at least one component ofv said organic mixture, 10
‘continuously withdrawing reaction mixture from
the reaction zone, separating the liquid phases
present, removing the phase containing the un
maintain said composition difference between the
total feed and the reaction mixture.
2. A process for continuously reacting an or
10 ganic liquid reagent with a second liquid re
agent in which its solution velocity is greater
than the velocity of the reaction between said
reagents under the existing conditions which
comprises continuously contacting said liquids
reacted organic compound and continuously re
turning such a part of the other phase as does 15
15 in a reaction zone containing a preponderance
of the liquid phase in which the reaction sub
,not contain reaction product equivalent to that
stantially takes place, ‘continuously withdrawing
formed in the reaction to said reaction zone.
7. A process for continuously reacting an or
reaction mixture from said reaction zone with
out substantially changing its composition, sep
20 arating reaction product therefrom equivalent
to that formed in the reaction and continuously
ganic liquid reagent with a second liquid re-/
agent with which it forms a reaction product of 20
low physical solubility ‘in said ‘second reagent
returning to said reaction zone at‘least a part
of the withdrawn phase in which the reaction
which comprises continuously adding said re
substantially takes place.
of said second reagent, continuously withdrawing
'
,
3. A process for'continuously reacting an or
agents to a reaction. mixture containing an excess
reaction mixture from the reaction zone without 25
ganic liquid reagent reactive with another liq
substantially changing its composition, stratify
uid reagent in which its solution velocity is great -- ing the withdrawn mixture into a phase contain-‘
‘ er than its characteristic reaction velocity under
ing reaction product and a phase containing said '
the existing conditions which comprises contin
second liquid reagent, continuously removing the
uously adding said reagents to a reactor main ~ phase containing the reaction product from the' 30
tained at a temperature at which reaction be
system and continuously returning the phase
tween the two reagents takes place,’ continuously containing said second liquid to contact with
withdrawing reaction mixture from said reac ' fresh reactants;
tor at a rate substantially greater than the total
8. A process for continuously reacting an or
rate of feed of said reagents without substan
ganic liquid reagent'with a second liquid reagent
tially changing the composition of said mixture, in which it has a low ‘physical solubility and with
separating material immiscible with the phase in which it forms a reaction product which is.sol-‘
which the reaction takes place, removing at least uble in said second liquid which comprises’ con
- a part of the reaction product equivalent to that tinuously-contacting said reagents in the pres
ence of an excess of a phase containing said 40
40 formed ‘in said reaction and continuously return
ing the remaining components of the withdrawn ‘second liquid reagent, continuously withdrawing
reaction mixture to the reactor.
‘
-_
g
.
reaction mixture therefrom without substantially
4. A process for continuously reacting an or
changing its composition, separating material im
ganic liquid reagent with another liquid reagent . miscible with said second liquidqreagent, remov
45 in which it has a limited physical solubility which ing from the system a part of the phase con-. -
comprises continuously contacting said reagents
taining said' second reagent containing reaction
in the presence of a reaction product thereof at a .product equivalent» to that formed in the re
temperature and at a pressure at which reaction
. between said reagents takes place with the for
50 mation, of a reacted mixture ‘made up of two
liquid phases, continuously stratifying and sep
’ . aratin'g said phases and retumingat least a part
of one of said phases containing said reaction
_
. product to contact with fresh reagents in the re
- 55
action
zone.
I
v
5. A process for continuously reacting an or
ganic liquid reagent with another liquid reagent
in which it has a limited physical solubility which
comprises continuously adding said reagents to
60 a reactor containing a substantial excess of one
reagent above the stoichiometric proportion in
which said reagents react while maintaining said
reactor at a temperature and at a pressure’ at
~which reaction between said reagents takes place
65 in the liquid state with the formation .of a re
acted mixture made up of two liquid phases, con
tinuously withdrawing reacted mixture from said
reactor, stratifying and separating said two‘liq
uid phases, removing one phase from the system,
70
recovering reaction product substantially equiva
lent to that formed in'the reaction and contin
uously returning the other of said phases con
taining said excess reagent to the reactor.
' 6. A process for continuously reacting at least
75 one component of» a mixture of organic com
action and returning the remainder of ‘said phase
to. contact with fresh reactants.
“
>
“a
.9. A process for continuously reacting an or- . "
ganic reagent with another reagent in which said
organic reagent has a solution velocity greater
than the velocity of_ the reaction between‘said
. reagents under the existing conditions which
comprises continuously adding said- reagents to:
a reaction zone maintained at a temperature at
which reaction between said reagents takes place
vand under a pressure at least ‘equal to the vapor. '
pressure of the most volatile component of the 60
reaction mixture, continuously/withdrawing re
action mlxture from said zone without substan
tially changing its composition at the ‘rate at:
which solution of said'organic reagent in the »
phase containing saidi‘other reagent is complete, . '
continuously separating material present in said
withdrawn mixture which is immiscible with said
liquid phase, continuously withdrawing’ from the
system reaction product at substantially the rate
at which it is formed, and continuously returning
such- a part of said liquid phase that, the average
time 'of residence thereof insaid reaction zone
. substantially corresponds to complete reaction.
10. A process for continuously producing a hy
drocarbon derivative which comprises continu 1.6
7]
. aioacar
ously feeding a hydrocarbon and a liquid reagent
cess of said reactive liquid reagent maintained
reactive therewith in which said hydrocarbon has ' at a temperature at which reaction takes place,
a low physical solubility to a reactor maintained continuously withdrawing reaction mixture
substantially liquid-full and at a temperature at‘ from said reaction zone withoutasubstantially
changing its compositiomremoving undissolved
said reagent takes place, continuously withdrawe hydrocarbon from the reactive liquid reagent, re- ing reaction mixture therefrom ,without substan-'-, . moving a part of said reactive liquid reagent
tially changing its composition at a rate sub-' ‘containing reaction, product equivalent to that
stantially greater than the rate of feed of hydro- “ formed and continuously returning the remain
der of said liquid reagent to said reaction zone. 10
10 carbon and reagent, separating material immis
which reaction between said. hydrocarbon and
cible with the phase in which the reaction takes
15. A continuous process of absorbing an ole
place, ‘continuously vremoving reaction product
?ne in an acid-acting medium which comprises -
substantially at the rate at which-it is formed - adding said ole?ne in the liquid phase and said
and continuously returning ‘at least -a part of acid-acting medium to an absorption product of
15 said phase in which the reaction takes place to
said ole?ne in saidvmedium, withdrawing the re
said
reactor.
'
'
‘
>
>
'
- suiting mixture at a higher volumetric rate than
that of said ole?ne and acid-acting medium ad
11'. A continuous process for producing hydro
carbon derivatives which comprises continuously ‘ ditions, separating an amount of the resulting '
feeding a- hydrocarbon and an aqueous reagent ole?ne absorption product equivalent to the acid
acting-medium- addition and returning the re 20
reactive therewith to a reactor containing pre
' ponderantly substantially reacted aqueous phase mainder of said absorption product to the ab
' »
‘
maintained at a temperature at which, reaction sorption unit.
between said hydrocarbon and said aqueous re
agent takes place and at a pressure at'which all
components of the reaction mixture are in the
liquid state, continuously withdrawing reaction
16. A continuous process of absorbing aniole- .
?ne in a mineral acid-acting acid which com
25
prises continuously feeding said ole?ne in the
liquid phase and said acid to a mixer maintained
substantially liquid-full and under strong agita» '
mixture. from said reactor without substantially
changing the composition thereof, separating any . tion, continuously withdrawing the resulting mix- hydrocarbon material which may be present un
ture to a separator .also maintained substan
tially liquid-full, ‘separating unabsorbed hydro- I v30
dissolved in the aqueous phase, continuously re
moving reaction product substantially at the rate carbons which may- be present from the result
at which it is formed and continuously returning ing oleflne absorption product, separating an- .
amount of‘ absorption productl substantially
aqueous’ phase to said reactor. "
12. A continuous process for producing a hy-' equivalent to the acid feed and returning the re- ‘ 3
drocarbon derivative which comprises continu- ‘ maining absorption product to the mixer. '
ously feeding a hydrocarbon and a liquid vacid
acting'medium to a reaction zone containing an
excess of said acid-acting medium maintained
at a temperature at which reaction between said
1'7. A continuous ‘process of absorbing the tcr- , '
tiary-base ole?ne content of an ole?nic mixture
containing less reactive olefines which comprises
continuously adding said mixture in the liquid '
'40 hydrocarbon and said aqueous reagent takes place
state ‘and an aqueous acid-acting medium to an
and at a pressure at which all components of the
reaction- mixture are ’in they liquid state, con
in said acid-acting medium at a temperature at
v tinuously withdrawing reaction mixture from said -
reactor without substantially changing the com
absorption product‘ of said tertiary-base ole?ne
which substantial absorption of the‘tertiary-base
position thereof, separating any hydrocarbon ma
ole?n'e takes place without substantial conversion
of the less reactive ole?nes present, continuously 40.
. terial which ‘maybe present undiss'olved in the
withdrawing the resulting absorption mixture, ~
. acid-acting medium, continuously removing re
separating unabsorbed material present, remov
action product substantially at the ‘rate at‘which, ing a part of the absorption product from thev '
it is formed and continuously returning aqueous ‘ system and continuously returning the remain50
phase to said reaction zone.
_
.
"
_
h
13. A continuous-process for producing a hy
drocarbon-sulfuric acid reaction product which
comprises’ continuously feeding‘ a hydrocarbon
‘der to contact with fresh tertiary-base ole?ne'
containing ole?nic mixture. and aqueous acid
acting ~medium.~
w
"
~
I
,
.
> _18. A continuous process of absorbing iso-'
butylene containing hydrocarbon in the vliquid
.and- a sulfuric acid containing phase’to a reac
tion ,zone'containing a preponderance of sub
stantially reacted sulfuric acid phase, while main
taining in said zone a temperature at which-re‘
action between said hydrocarbonan'd' sulfuric
acid takes place ‘and, at a pressure at which all
; components of the reaction mixture-are in the
~ liquid state, continuously withdrawing reaction.
about 40% to about 80% strength at a tempera
ture at whichsubstantial absorptionof iso
butylene is effected without substantial poiymer-'
ization in the presence of a substantiallylarger
from the reaction zone, separating hy
drocarbon undissolved in the sulfuric acid, con?
tinuously removing a part of the sulfuric acid
phase containing reaction product equivalent to
that‘formed and continuously returning the re
suiting reaction mixture at a substantially higher
rate than that "at which the isobutylene and
acid solution are fed, continuously separating'un- ‘
absorbed hydrocarbons from the withdrawn mix
'mainder of the ‘sulfuric acid
”actionzone.
'
-
"
said ref
-
phase with an aqueous sulfuric acid solution of
volume of an absorption product of isobutylene .60
in said acid, continuouslylwithdrawing the-re
ture, removing a part of ‘the resulting lsobutylene
absorption product equivalent to the feed and '
continu usly .returningthe remainder. to con-'
14. A continuous process for producing an oieé Y tact with resh isobutylene and sulfuric acid solu
70 fine "derivative which comprises continuously tion at a rate atv which-the ‘composition of
feeding oleflne containing hydrocarbon material absorption product isn'ma'intained
in the liquid state and a liquid reagent reactive
‘therewith to a reaction zone‘ containing an’ extv
1
i
constant.
.' l]
_
_
I_
MeLDEANELY; '
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