CA2526151A1 - Process and equipment to produce phenol from benzene - Google Patents

Abstract

Existing phenol production via the cumene or other processes, are complicated, multiple staged and energy consuming, producing ketone by-products. The typical yield is about 5%
per pass by wt. A direct oxidation process that would eliminate the need for any reagents such as H2, gases, or Nitrous Oxide is most sought whereby;

(see above formula) A recent development for a single stage process uses a Palladium membrane as a passive catalyst in a reactor chamber, reporting up 16% yield per pass. However, this process also generates hexane, cyclohexane and toluene as by-products in reactor temperatures in the order of 250° C. This one step process requires O2, & H2 gases and is very temperature sensitive. The volume of gases introduced into the reactor are also critical. In addition, the benzene must be delivered in it's gaseous state. The process demonstrates that the benzene ring is indeed reactive with an oxygen ion, but not with the O2 gas molecule. This apparatus was developed by The National Institute of Advanced Industrial Science and Technology (AIST) Laboratory for Membrane Chemistry in Japan.

Description

Figures: (C.~u Ct S

Pai7es: a 90, "1 TJnsc=able items receisred with this application (Request ori7inal docurnents in File Prep. Section on the 10th Floor) Documents recus avec certe demande ne pouvant ztre bala; es (Comm-,,nder [es documents ori<nnau-x dans la sec-,ion de preparation des dossiers au IOie:ne etaae) Edward Melcarek, C.E.T.
Harry Laur, Sam Turtle, Hypothesis:
A two step oxkiaYon proCess is possibie if water is used as the sounce of free oxygen ions and a reaction carrier medium.
In general, the proposed two step route in a singie reactor, is thus, without added catalysts or heat.
~ !-hO ----- H + a-i qmdriLm (mmcb b HbfO
Bec~dyds ;
O84V Q Fartictien Fbacdm at PeMadkrnAnmb ~ 4CH--- O; + O; +21-k0+4e ReeOgikmQertieralia~
in'Tfa ~#aeN~~elic F9eld vAh18Wit SorMoetloi , pqAed Baras~e Fhad ~
~ C8 h~s + ~ ~ ~
Bam ReeC~gr -a31-13 *V ksi CB t-t 0-i Ftedktattiaulmodihe MeckrriArrods Rather than trying to make the benzene more reactive with eiectrophiies and reagents, this method takes advantage of the benzene's unusuat etebiiity. The cyciic conjugated pi-bonds a,re enbOtropiC
resonance structures requiring that substitution, not additison, would be the norm when a neattion does occur. The substitution in this oxidation pracess is simply an oxygen for a hydrogen ion. The oondidons for this reaction to occur requires that the hydrogen pi-bond resonance structure in the benzene ring be parttaty ionized without cxampromising the sitobility of the ring.
This can be accomplished with the addftiort of heat, or, as in this apparatus, with the forced dynamic periodic excursion of the moiecuie across a static magnetic field, which allows extreme control of said ionization.
The oxygen generated by eiectroiysis, Is also forced across the field Nnes, producing the oxy ion reactive species at the palladium anodesurface and benzene / water interface.

The advantages;

= All static & dynamic parameters are electronicaly controlled.
= The palladium Anode functioneas both the cataiyst and Oxy ion source.
= No reagents are required other than distilled water and electrical power.
= Room temperature operation, no added heat required.
= Uquid phase process throughout.
= No unwanted process by-products.
= Benzene remains In its' found stable state into the oxidation process.
= Generated Phenol is diffused.kt the water carrier aNowing simple control and transfer.
= Continuous process can be easily sc:aled for production.
= Hydrogen gas is generated as marketable by-product to offset operating costs.
Page2of1 Edward Melcarek, C.E.T.
Harry Laur, Sam Turde, Apparatus;

kft Fbovw s#Y
o-4D\oc a Vt+c G~TLbB

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, ...._ ........ ....... ...... _._.

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j Ekcbcd3 1EU* LYARsyb ~ ~ La~i,~fasoLae-0 0 0 0 "bwmGLnwllbne'Anp q IODMQ/N407BWt ...:. ................... .-....................................
............................ ......................
~----------------~
~e s1W
-14B -4B\M ( Theory of the Method; The Oxygen Source. [ electrical energyy + 2 H20 -> 02 +

2 H2 j e~ - +
- - - - - - - --------Fi2 Qz H O@
nn, nn =H+ Q,--4' H2o-) The standard model of water electrolysis;
Page 3 of 1 Edward Melcarek, C.E.T.
Harry Laur, Sam Turde, eo~oG, HadedrbwesaFbMdim vdl,K ~KilgidoFlAd Ird oedeera~nsF~pbTo~
eaWg Aou.AolM Wr,q tominsrioMim K*Cidof-Idd -- t~ ~ ~........ aCFFER Bwmas CB F!S ~ ; p R';RTF + O
as m SUikokn ini-b Fb..b Puaic, eccwmcb ; -- cbi-a + o;
+ + ~ ;
ResoV
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arfENLPECN
n~a< nAI3-jqqooL Lcx3nLcr4q_ 1"**Ecr~
.. ~ C~~H=r ACFCr:B aLx LnEB

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Paga 4 of 1 Edward Meicarek, C.E.T.
Harry laur, Sam Turtle, A water electrolyzing potentiai: of 100 Votts and is eppiied through tWro eteotrodss irnmenaed in the water coiumn. The palladium anoft eiectrode is hoNow to ailow the benzine to be infused at the bottom of the watar ooiumn. The benzwepercOiates up along the wais of the paUadiwn awft electrode through the water column where it encounters free oxygen ions generated by the water electrotysis process in the twsverse magrretic fieid:
The palladium anode acts as both an eiectroiytic source of oxy Ions and as an passive catalytic surface whereupon oxidation takes place.
In the presonce of the magnetic flux, at the surface of the palladium anode, oxygen gas 02, molecules are not agowed to form. tnstead, as oxygen. atoms are eiectroiyticaiiy liberated from the water molecuie, they are driven across the sWc magnetic field iines by the vibrating water column, ionizing them, & thereby prevertting the fom7atton of 02 gas mote$. Free oxy ions are now free to react with the partiaiiy ionired benzene mole in the contact with the paiadium surface which is a catalyst. Ozone also will not form in the water carrier.

OONDfflONS GENERATED
PER1oDIC DISPLACEMENT AT SURFACE OF PALLADIUM
MAGNITUDE WITH XDCR. AN~DE
F LORENTZ FORCE LAW
F=qvXB
Y x Y X
Q+ 8PECIEB' PRODUCTION PALLADIUM ANODE
z PROPERTIES z D(*AIN

.,\
'-.
B MAG FLUx j ~. B MAG FLUX
DENSITY I
k~ ~..
ve ~
INDUCED NET CHARGE
IMPARTED TO OXYGEN

l~w NOTE: ANODE ACTS AS BOTH CATALYST
AND REACTlVE SPECIES SOURCE
IN REAL TIME.

Magnetic Flux Benzene Phenol / ' Q+
~ ----- '--- OH
0 Palladium Cs Hs Catalyst, No Heat Cs Hs OH
t Transducer Displacement Page5ofl Edward Meicarek, C.E.T.
Harry Laur, Sam Turde, The acoustic excitation is excluded in the cathode region where hydrogen gas is generated. This allows it's passage through the static magnetic field **s to the surface of the water column without any reaction with the diffused phenol in the water. This is accomplished by isolating the anode by means of a simple glasss tube as shown in the. iliuetradons.
The formed phenol diffuses throughout:the water column in the beaker, and would indeed re-react with the hydrogen to form water and bemme in a cbsed k~ wiih little or no net yield.
This re-reaction is prevented by means of aooustic, lensittg which blocks the acoustic energy in the cathode ring region and by segregating the anode region with the glass tube.

TRANSDUCER F LORENTZ FORCE LAW
qvxB
DISPLACEMENT F=
REMOVED
IN CATHODE REf310N Y Y
X X
PLATINUM CATHODE
REVERSE REACTION Z PROPERTIES Z
DOMAIN

B MAQ FLUX

+Ve qv i ZERO NET CHARGE

& PHENOL MOLE
CONDITIONS GENERATED
AT SURFACE OF PLATINUM
CATHODE

Phenol Forbidden Reverse Reaction Benzene with H2 atPiatinum Cathode.
/ \ 0 H + H , --~ H 20 +

Blocked Sonification in C6 Hs OH H: Forming region at C6 H6 Platinum Cathode Thus, the reverse reaction does not occur with the transducer dispiacement removed in the cathode region of the reactor glmware. Hydnogert Is freie to ~pass through the magnetic field to the top of the water column without reacting with the phenol / water mixture.

The yield is expected to be greater than 50 /a per pass or greater, and will be a function of the variable parameters of the apparatus.

There are four variable parameters in this magneto-kinetic apparatus.
Benzene Volume injection rate. [ Hand operated 50 cc Syringe ]
Electrolysis Voitage, (Oxygen volume from the water ) [ Voltage to Anode &
Cathode.]
Magnetic Flux Density. ( Oxy Ion g8neration rate ) [ VoQage to Electro-magnets.] Displacement Amplitude across Magnetic Field. [ AC Voltage to Transducer ]

Page6of1

Claims (7)

Claims;

1. An electro-dynamic process that passively oxidizes benzene to form phenol using nothing more than distilled water and electricity. There are no exothermic or endothermic reactions.

2. A process where there are four physical reactions occurring in the apparatus simultaneously;
Those being;

.cndot. The electrolysis of water to form free oxygen and hydrogen gas with applied voltage.
.cndot. The ionization of oxygen atoms after liberation from the water in the magnetic field.
.cndot. The periodic ionization of the benzene molecules across said magnetic field.
.cndot. The passive oxidation of the benzene mole with a free oxygen ion at the surface of a palladium electrode also acting as a catalyst.

3)- A process whose functional embodiments are described on pages 2, 3, 4, 5, & 6.

4)- A process whose variable functional parameters are;

.cndot. Magnetic Flux Density; 0 - 5,000 Gauss. Variable.
.cndot. Electrolysis Voltage; 10 - 160 VDC, Variable.
.cndot. Benzene Excursion Amplitude across Magnetic Field; 0 - 20 microns Variable.
.cndot. Transducer Frequency; 0 - 18 kHz. Variable.

5)- A process where the only products are phenol and hydrogen gas.

6)- An anode that acts as both catalyst and a reactive oxygen ion source.

7)- A device whose process attributes are generated with an ultrasonic transducer, a voltage, and a static magnetic field.