Europaisches Patentamt

European Patent Office

Office europeen des brevets © Publication number: 0 5 6 6 7 9 8 A 1

© Application number: 92308394.3

@ Date of filing: 15.09.92

E U R O P E A N PATENT A P P L I C A T I O N

394.3 © int. Ci.5; C07C 37/20, C07C 3 9 / 1 6

© Priority: 20.04.92 US 870973 © Applicant: TEXACO CHEMICAL COMPANY 3040 Post Oak Boulevard

@ Date of publication of application: Houston, Texas 77056(US) 27.10.93 Bulletin 93/43

@ Inventor: Knifton, John Frederick © Designated Contracting States: 10900 Catskill Trail

DE ES FR GB Austin, Texas 78750(US)

© Representative: Brock, Peter William et al URQUHART-DYKES & LORD 91 Wimpole Street London W1M 8AH (GB)

© Bisphenol a production using acid modified clay catalysts.

© Bisphenol A can be synthesized by reacting phenol with acetone in the presence of a catalyst, comprising a montmorillonite clay having the structure:

Mx/„n+ y H2 0(AI4-xMgx)(Si8 )O20 (OH)*

where M represents the interlamellar cation, and x, y and n are numbers, which has been rendered acidic by pretreatment with one or more acids selected from hydrogen fluoride, fluorosulphonic acids or anhydrides, and mineral acids. The reaction is carried out at a temperature of from 20 to 200 °C and a pressure of 0.1 to 7.0 MPa.

00 Oi IV CO CO m

Rank Xerox (UK) Business Services (3. 10/3.6/3.3. 1)

EP 0 566 798 A1

This invention relates to methods of producing bisphenol A. More particularly, it relates to a method of producing bisphenol A from acetone and phenol using montmorillonite clay modified with an acid.

The reaction of phenol and acetone in the presence of a catalyst to produce bisphenol A is known in the art. Catalysts which have been used include cation exchange resins and acids.

5 Generally, the use of acids represents the older method for the condensation of phenol with acetone. Representative acids include an aromatic sulphonic acid (DE-A-281 1 182 and US-A-4387251), volatile acids (US-A-2623908), strong mineral acids, such as HC1 or H2SO+ (US-A-2359242), hydrochloric acid (US-A- 4517387), H2SO4 or HC1 and 2-(4-pyridyl)ethanethiol (JP-A-57-1 18528), concentrated HC1 (JP-A-60-38335) and hydrogen chloride (US-A-416921 1).

10 Acidic catalysts have several disadvantages. They necessitate construction materials which are consid- erably more expansive, they represent more of an environmental impact due to the cogeneration of waste materials, and product purification is more costly.

A number of cation exchange resins have been used to convert phenol and acetone into bisphenol A. For instance, EP-A-01 44735 makes use of a sulphonated polystyrene ion exchange resin having ionically

15 bound (25-35 mol%) N-alkylamino-organomercaptan groups. Acetone conversions of 50-70% are observed. The use of clays as catalysts for selected applications is known in the art. An article entitled "Catalysis:

Selective Developments" Chem. Systems Report 84-3, 239-249, section 3,4320, discusses the unusual properties of smectite clays which make them of interest as catalysts. These compositions are layered and exhibit a 2:1 relationship between tetrahedral and octahedral sites. In addition the combination of cation

20 exchange, intercalation and the fact that the distance between the layers can be adjusted, provide interesting possibilities.

An article by F. Figueras, entitled "Pillared Clays as Catalysts", in Catal. Rev.-Sci. Eng., 30, 457 (1988) discusses methods of modifying clays and the effects of the modifications. At page 472, there is a discussion of the method of drying, i.e. air drying or freeze drying, which can affect the macroporosity and

25 adsorption capacity of the resulting product. The author concludes the thermal stability of pillared clays can be improved to reach 800 0 C using information available with respect to intercalation and drying methods.

Figueras notes (page 481) that the acid strength of montmorillonites was found to be higher than that of Y-zeolites and, in the case of the clays, Bronsted acidity appears to be weaker than Lewis acidity. The author describes three kinds of acid sites known to exist at the surface of clay and suggests the

30 coexistence of several types of acidity makes the localization of acid sites more difficult than in well- crystallized structures.

There are two reviews of the catalytic activity of pillared clays by T. Matsuda and E. Kikuchi, entitled "Acidic Properties of Pillared Clays in Relation to Their Catalytic Behaviour", in Proceedings of International Symposium on Acid-Base Catalysis, Sapporo, Nov. 28-Dec. 1, 1988. In Ch. 3.11 these authors observed

35 Bronsted acid sites are responsible for isomerization whereas both Bronsted and Lewis acid sites can catalyze disproportionation. Other pertinent findings were that Bronsted sites are far more active than Lewis sites, but studies would indicate an irreversible change of Bronsted acidity to Lewis acidity in the course of high temperature calcination, (page 354). The authors concluded that cracking of a compound such as cumene, depended only on the acidic properties, but disproportionation activity was affected by the pore

40 structure in addition to acidity. This was thought to relate to the fact that pillared montmorillonite had regular micropores, while pillared saponite had macropores. In addition saponite is tetrahedrally charged clay with Al cations substituting for Si cations. In montmorillonite, in contrast, Mg cations are octahedrally substituted for Al cations. At page 352, it is stated that cracking acidity is satisfactorily related to Bronsted activity while it is difficult to find any relationship between the disproportionation activity and the acidic property.

45 There are two reviews of the use of pillared, cation-exchanged and acid-treated montmorillonite as catalysts for certain organic reactions by J.M. Adams et al., J. Inclusion Phenomena, 5, 663 (1987), Applied Clay Science, 2, 309 (1987). These clays display Bronsted and Lewis acid activities. It is noted that while some cationic species are stable in solution over a wide concentration and pH range, others are not, particularly solutions containing aluminium. It is noted that it is difficult to ensure a reproducible Al3+ clay

50 and moreover, since workers have used slightly different exchanging and washing procedures, a compari- son between related experiments is hindered. Commercial acid-treatment is carried out using concentrated hydrochloric, sulphuric or phosphoric acids. The concentration of the acid and the time of the treatment is variable. Sometimes the excess acid is removed by washing, whereas in other products, this is not the case. Therefore there is a great variety in the type and activity of acid-treated clays.

55 Montmorillonites have been used as catalysts for the reaction of straight chain alk-1-enes to ethers, and for alkenes plus alcohols. In the latter, primary alcohols gave high yields, secondary less and tertiary alcohols only trace amounts. The Al+3 clays have efficiencies of one third to one half of Amberlyst® 15 in reactions of this type without solvent or using 1 ,4-dioxane.

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EP 0 566 798 A1

The acid-treated clay K-306 can be used to convert methanol and ammonia into methylamines. Acid- treated clays have also been used to convert cumene hydroperoxide into phenol and acetone.

With respect to the production of bisphenol A, most recent research and development has been concerned with BPA separation and purification. There is an increasing demand for high purity bisphenol A

5 for polycarbonate resin manufacture. Catalyst enhancement is also of interest, see: "Bisphenol A and Alkylated Phenols," SRI PEP Report No. 192 (Dec. 1988) Section 4.

Processes using acid catalysts, such as anhydrous HC1, require extensive recovery facilities, product purification and waste treatment. In addition, the presence of highly corrosive streams requires the use of costly corrosion resistant construction materials.

io The newer processes using a cation exchange resin catalyst have an advantage over the acid catalysts in that the resins are non-corrosive and require no catalyst recovery, Ibid, p. 5-1.

Though they represent an advance over the use of acid catalysts, the resins still have disadvantages. In a typical resin process design, the process unit is divided into three sections, for condensation, separation and rearrangement respectively, and the operation of the condensation reactor is limited to <120°C,

is because of the low thermal stability of said resins. There is a necessity for extensive recycling of unreacted phenol/acetone, water removal, crystallization and purification.

It would be a distinct advance in the art if bisphenol A could be prepared in one unit using a more thermally and hydrolytically stable catalyst, which did not require phenol/acetone recycling, pretreatment of the feed for water removal, etc. It would also be desirable if it did not use corrosive chemicals or require

20 handling and disposal of salts constituting by-products. It would be particularly helpful commercially if the catalyst exhibited high thermal stability and extended catalyst life. Such a process would be especially attractive since it would be simpler to operate than processes currently used in the art.

It is an object of the instant invention to provide a one-step process for the synthesis of bisphenol A using a catalyst system which accomplishes the reaction in one step and exhibits extended life.

25 This invention provides a method for the synthesis of bisphenol A by reacting phenol with acetone in the presence of a catalyst, comprising a montmorillonite clay having the structure:

Mx/„n+ y H2 0(AI4-xMgx)(Si8 )O20 (OH)*

30 where M represents the interlamellar (balancing) cation (preferably sodium or lithium), and x, y and n are numbers, which has been rendered acidic by pretreatment with one or more acids selected from hydrogen fluoride, fluorosulphonic acids or anhydrides, and mineral acids. The reaction is carried out at a temperature of from 20 to 200 ° C and a pressure of 0.1 to 7.0 MPa.

Preparation of the product of this invention may be carried out typically by reacting an excess of phenol 35 with acetone in the presence of an acidic clay. The reaction can be represented by the following:

40

45 The product, bisphenol A, is isolated in high purity by fractional distillation. Bisphenol A is an important specialty chemical. Bisphenol A is in demand as a raw material for manufacturing polycarbonate and epoxy resins. The polycarbonate resins are used for glazing, computer housings, electric parts, compact disks and appliances. Epoxy resins are used for surface coatings, laminates, composites, adhesives, mouldings and castings.

50 The molar ratio of acetone to phenol can vary from 10:1 to 1:100. The preferred molar ratio is about 1:10.

As stated the catalyst comprises a montmorillonite clay which is acid activated and modified with an acid selected from hydrogen fluoride, fluorosulphonic acids and anhydrides, and sulphuric acid, plus combinations thereof. Suitable fluorosulphonic acids or anhydrides include fluorosulphonic acid itself,

55 trifluoromethanesulphonic acid (triflic acid) and trifluoromethanesulphonic anhydride. The montmorillonite clays are used in the present application in an acidic form. Acids activate

montmorillonites by attacking and solubilizing structural cations in the octahedral layers. This opens up the clay structure and increases surface area. These acid-treated clays act as strong Bronsted acids. Generally

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EP 0 566 798 A1

strong mineral acids are used to activate the clay, for example, sulphuric acid and phosphoric acid. As noted in the above-mentioned Matsuda review, there is an indication that Bronsted sites are more active, but have a tendency to convert to Lewis acid sites as temperature increases during calcination of pillared clays. The clays are effective in the form of granules, powders or extrudates.

5 The acid-treated montmorillonite clays used according to the present invention, upon which the triflic acid or hydrofluoric acid are deposited, should have acidities of at least 1.0 mg KOH/gm, and preferably 5 to 100 mg KOH/gm, titrated to a phenolphthalein end point. Their surface area should be at least 30 m2/g, and preferably 200 to 1000 m2/g. Their moisture content should be limited also, whereby upon heating at 105 °C the weight loss is generally less than 20 wt%, but may be higher under certain circumstances.

io Illustrative examples of suitable acidic montmorillonite clays include clays in granular form, such as Filtrol Grade 24, having a 20-60 mesh size (0.25-0.84 mm) and Grade 24 Superacid Clay. Filtrol Grade 24 is manufactured by Engelhard and has an acid capacity of 25 mg KOH/g. Grade 24 Superacid Clay, also from Engelhard, typically has acidities of 33 to 93 mg KOH/g.

Where the montmorillonite clay or acid-pretreated montmorillonite clay, as described above, is impreg- 15 nated with triflic acid or hydrogen fluoride, the clay is generally treated with from 0.01 to 10% triflic acid or

HF, and preferably the clay is impregnated with from 0.1 to 1.0% triflic acid. The following Examples demonstrate that about 0.1 to 1.0% is an effective amount.

Where hydrogen fluoride is deposited on acidic montmorillonite, 0.1 to 10% is a preferred effective amount.

20 An effective amount of triflic acid or hydrogen fluoride would be sufficient to produce an acidity of the catalyst in the range of 1 to 100 mg KOH/g.

Preparation of bisphenol A is preferably conducted in a fixed bed, continuous flow reactor, operated upflow.

The temperature of the reactor is from 20 to 200 °C, preferably 30 to 140°C. The preferred temperature 25 depends on the choice of conditions, and the most effective temperature is usually from 110 to 130°C. The

pressure can be from 0.1 to 7.0 MPa (atmospheric to 1000 psi) and is preferably about 2.17 MPa (300 psi). Typically the bisphenol A is generated continuously in up to ca. 10+ wt% concentration in the crude

product liquid effluent. Acetone and phenol conversions are significant. Fractional distillation yielded pure bisphenol A wherein

30 two isomers are present in a ratio of about 3:1 . These yields are achieved at a total liquid hourly space velocity (LHSV) of 1 to 10 under mild

conditions. Here LHSV is defined as follows:

35

40

Vo lume of T o t a l L i q u i d Feed R u n LHSV = T h r o u g h t h e R e a c t o r Pe r H o u r

Vo lume of C a t a l y s t in R e a c t o r

Conversion of acetone and phenol (wt%) is estimated in the following examples using the equation:

45 ^nn f Wt% Cone , of A c e t o n e or P h e n o l in P r o d u c t \ inn 100 - ( J x 100 \ Wt% Cone , of A c e t o n e of P h e n o l in Feed J

50 Yields of bisphenol A (mole%) are estimated from:

M o l e s of B i s p h e n o l A in P r o d u c t L i q u i d 1Q0 55 M o l e s of A c e t o n e or P h e n o l in F e e d

4

EP 0 566 798 A1

50

Product analyses were primarily by gas liquid chromatography (glc) and gel permeation chromatog- raphy (gpc).

EXAMPLE 1

To 85g of a neutral montmorillonite clay (Engelhard Grade 2C Powder, dried at 175°C in vacuo) was added a solution of trifluoromethanesulphonic acid (10.0g) in dried acetone (100cm3). The mixture was stirred for 24 hours under a nitrogen blanket, and filtered and the solids were washed first with acetone and water, then dried in vacuo at 40 ° C overnight and at 150 ° C for 4 hours.

70 The recovered pale yellow powder was found to contain by analysis: H20 = 0.73% Acidity = 10.6 mg KOH/g

EXAMPLE 2 75

Synthesis was conducted in a 150cm3 capacity tubular reactor constructed of 316 stainless steel, operated upflow and mounted in a furnace, controllable at ±1.0 °C and fitted with liquid feed pumps, a pressure regulating device and equipment for monitoring temperature, pressure and flow rate.

The reactor was charged at the beginning of the experiment with 150cm3 of a sulphuric acid-treated 20 montmorillonite clay, in granular form (Sample 104589 from Engelhard) having a titratable acidity of 33 mg

KOH/g. The catalyst bed was then treated with a phenol/acetone (10:1 molar mix) upflow, at a rate of 150cm3/hour, while the reactor was held at 50 °C, with a total pressure of 2.17 MPa. Samples of crude product effluent were collected on stream, and analyzed by glc and gpc. Typical analysis data are summarized in Table I.

25 Catalyst performance over a range of temperatures (50°-110°C) was also measured, after reaching equilibrium conditions. Summary data for these additional runs are also given in Table I.

Finally, samples of each product were stripped under vacuum to remove lights plus unreacted acetone, then reanalyzed for bisphenol A content by gpc. These data are also included in Table I.

30 EXAMPLES 3-5

Following the procedures and practices of Example 2, the synthesis of bisphenol A from phenol and acetone was demonstrated using the following acidic clay catalysts:

Example 3 A montmorillonite clay that had been treated with trifluoromethanesulphonic acid (triflic 35 acid) such that the concentration of triflic acid (TF) on the formulated catalyst was 0.1%

and the titratable acidity was 1 1 mg KOH/g (provided by Sud Chemie). Example 4 A hydrogen fluoride (HF) treated clay that had previously been treated with sulphuric acid,

where the HF concentration of the finished catalyst was ca. 4.5% (produced by Engel- hard).

40 Example 5 Another sulphuric acid-treated montmorillonite clay with a titratable acidity of 93 mg KOH/g (provided by Engelhard).

The glc and gpc analyses of the crude product effluent products and stripped products from these three Examples are summarized in the accompanying Tables II to IV.

Fractional distillation of the crude product liquid from Example 3, in vacuo, yielded pure bisphenol A. 45 NMR and IR analyses of this bisphenol A fraction showed the I to II isomer ratio to be 74:26.

HO ( f ) ) C ( ( J ) OH HO

CH3 «3C HO/

S t r u c t u r e I S t r u c t u r e I I 55

5

EP 0 566 798 A1

EXAMPLE 6

This example illustrates an extended catalyst life for a sulphuric acid-treated clay catalyst. Synthesis procedures were described in Example 2. The continuous reactor system was charged with

150cm3 of sulphuric acid-treated montmorillonite clay that had previously been dried in vacuo at 175°C having a titratable acidity of 45 mg to KOH/g and a water content of 0.3%. A feed mix of phenol/acetone (10:1 molar) was passed upflow over the catalyst at a rate of 150cm3/hour, at 130°C and a total pressure of 2.17 MPa. Samples of crude product effluent were collected on stream, analyzed by glc and gpc. The results are summarized in Table V.

< \ to c

- I I «n n o>

oo in

i

o o

I o m cm > rH n r-

EP 0 566 798 A1

TABLE V

bisphenol A

Ex. Catalyst Sample Time On Stream Product Composition (gpc, %) (Days)

BP A PhOH

6 H2S(VCIay 1 3 6.3 93.7 3 7 4.0 96.0 4 10 3.5 96.5 6 15 2.3 97.7 7 18 2.2 97.8

Claims

1. A method for the synthesis of bisphenol A by reacting phenol with acetone in the presence of a catalyst, characterised in that the catalyst is a montmorillonite clay having the structure:

Mx/„n+ y H2 0(AI4-xMgx)(Si8 )O20 (OH)*

where M represents the interlamellar cation, and x, y and n are numbers, which has been rendered acidic by pretreatment with one or more acids selected from hydrogen fluoride, fluorosulphonic acids or anhydrides, and mineral acids, and in that the reaction is carried out at a temperature of from 20 to 200 °C and a pressure of 0.1 to 7.0 MPa.

2. A method according to Claim 1 characterised in that the montmorillonite clay has been treated with sulphuric acid and has an acidity of 1.0 to 100 mg KOH/gm.

3. A method according to Claim 2 characterised in that 0.1 to 10% wt% of hydrogen fluoride is deposited on the sulphuric acid-treated montmorillonite clay.

4. A method according to Claim 1 characterised in that the fluorosulphonic acid is fluorosulphonic acid or trifluoromethanesulphonic acid.

5. A method according to Claim 4 characterised in that 0.1 to 10% by weight of trifluoromethanesulphonic acid is deposited on the montmorillonite clay.

6. A method according to Claim 5 characterised in that the acidity of the acid-treated clay is from 2 to 15 mg KOH/g.

7. A method according to Claim 1 characterised in that the fluorosulphonic anhydride is trifluoromethanesulphonic anhydride.

8. A method according to any one of Claims 1 to 7 characterised in that the maximum operating temperature is 30 to 140°C.

11

P 92 30 8394

DOCUMENTS CONSIDERED TO BE RELEVANT Citation of document with indication, where appropriate, Relevant CLASSIFICATION OF THE -ategory of relevant passages to claim APPLICATION (Int. C1.5 )

X US-A-2 862 976 (A C DUBBS ET AL) 1,8 C07C37/20 * column 2, line 64 - column 3, line 44 * C07C39/16

k EP-A-0 331 173 (MITSUBISHI PETROCHEMICAL) 1 * page 3, line 21 - page 4, line 9 *

A PATENT ABSTRACTS OF JAPAN 1 vol. 13, no. 39 (C-563)(3387) 27 January 1989 & JP-A-63 238 032 ( MITSUBISHI PETROCHEMICAL CO. ) * abs t rac t *

A EP-A-0 251 169 (UNION CARBIDE) 1 * page 3, line 29 - page 5, line 4 *

A US-A-3 496 239 (L A HAMILTON ET AL) 1 * claims; examples *

A nF-R-1 051 864 (FARBENFABRIKEN BAYER) 1 * column 1, line 30 - line 41 * technical fields

SEARCHED (fat. CI. 5 )

C07C

The present search report has been drawn up for all claims Plata of twck DtftafcuylitiinoftkiiMKk Exwlatf

THE HAGUE 18 JUNE 1993 HEYW00D C.J .

CATEGORY OF CITED DOCUMENTS T : theory or principle underlying the invention E : earlier patent document, but published on, or X : particularly relevant if taken alone after the filing date Y : particularly relevant if combined with another D : document cited in the application

document of the same category L : document dted for other reasons O : non-written disclosure * s member of the same patent family, corresponding P : intermediate document document