Transalkylation of alkylated phenols

Abstract

A transalkylation process is described that uses a catalyst comprising a three-dimensional 12-ring zeolite with a combination of small and large pores, which increases the conversion of alkylphenols from coal-derived liquid streams to phenols, cresols, and alkylbenzenes compared to a catalyst comprised of HZSM-5 zeolite.

Description

[Background technology]

[0001] Low and medium temperature coal tar contain abundant amounts of valuable oxygenates, such as phenols, cresols, and xylenols, in the feed, along with the less desirable longer chain alkylphenols.

[0002]

[0002] Direct dealkylation can be used to convert alkylphenols, but there are several problems associated with the process. When direct dealkylation is carried out without a catalyst, the process temperature is in the range of 700-900°C. This can lead to dealkylation of phenol by pyrolysis at high process temperatures. This is very energy intensive due to the high process temperature. In addition, it is usually not selective due to the loss of hydroxyl groups. Catalytic dealkylation can be carried out under much milder conditions. At temperatures of 300-400°C, ethylphenol and propylphenol can be dealkylated over ZSM-5 zeolite to produce phenol and ethylene / propylene. However, water usually needs to be co-fed to prevent significant catalyst deactivation. In addition, the dealkylation of cresols is relatively difficult and phenol selectivity can be an issue. Summary of the Invention [Problem to be solved by the invention]

[0003]

[0003] Therefore, there is a need for an improved process for converting alkylphenols in coal tar feeds to phenol and xylenes. Transalkylation of alkylphenols with co-reactants (e.g., co-reactants such as benzene or toluene) can help prevent loss of hydroxyl groups since the process temperatures are less severe, and also produces more valuable alkylbenzenes as co-products compared to the ethylene / propylene produced by dealkylation. [Brief description of the drawings]

[0004] [Figure 1] FIG. 1 is a comparison of the conversion of 4-ethylphenol in a transalkylation process using various catalysts, including zeolites. [Diagram 2]

[0005] FIG. 1 shows a comparison of 2,6-xylenol conversion in a transalkylation process using various catalysts, including zeolites. [Diagram 3]

[0006] FIG. 1 shows a comparison of 4-ethylphenol conversion in a transalkylation process using HZSM-5 SAR80 and HBeta SAR25 zeolites with N2 and H2 co-feed. [Figure 4]

[0007] FIG. 1 shows a comparison of the conversion of (A) ethylphenol and (B) xylenol from a cresylic acid feed in a transalkylation process using various catalysts, including zeolites. [Diagram 5]

[0008] FIG. 1 shows a comparison of (A) ethylphenol and (B) xylenol conversion from cresylic acid feed in a transalkylation process using HBeta SAR25 (80%) compared to HBeta SAR25 mixed with other zeolites (20%). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005]

[0009] Coal-derived feed streams, such as low temperature coal tar, medium temperature coal tar, high temperature coal tar, cresylic acid, or crude phenol mixtures, contain phenol, alkylphenols (methylphenols (cresols), ethylphenols, dimethylphenols (xylenols), propylphenols, butylphenols, methylethylphenols, etc.), and heavier alkylphenols (e.g., indanol and naphthol). Coal tar is derived from the process of carbonization and gasification of coal and is classified based on the temperature used in the process (400-600°C (low temperature), 600-1000°C (medium temperature), and >1000°C (high temperature). Cresylic acid is a generic term referring to a combination of phenols and alkylphenols and can be obtained, for example, from either coal or petroleum processing. Crude phenol mixtures can be obtained, for example, from coal tar oil processing and purification of phenol-containing waste from coke ovens, low temperature carbonization, and hydrogenation plants. The composition of the feed stream will vary depending on its source.

[0006]

[0010] Undesirable longer chain alkylphenols in the coal-derived feed stream can be separated into the coal-derived liquid stream and converted by transalkylation to valuable products such as, but not limited to, phenol, cresols, and xylenes. The alkylphenols in the coal-derived liquid stream can be transalkylated with co-reactants (e.g., co-reactants such as benzene and / or toluene) to transfer longer chain alkyl groups (e.g., ethyl, propyl, butyl, etc.) to obtain phenol and alkylbenzenes as new products. Alkylbenzenes, such as xylenes, ethylbenzene, and ethyltoluene, are in demand for industrial processes and are more valuable compared to toluene. In some cases, it has been identified that phenols with methyl groups, such as cresols, xylenols, and trimethylphenols, are not easily transalkylated with aromatic compounds, thus leaving the valuable phenols intact.

[0007]

[0011] WO2019177458 (WO'458) showed that 4-propylphenol (a model feed of phenol derived from biomass lignin) could be transalkylated with benzene using HZSM-5 catalyst. Several other zeolites were tested (HMOR and HY), but were not as active as HZSM-5.

[0008]

[0012] In "Conversion of alkylphenol to phenol via transalkylation using zeolite catalysts," Yoshikawa et al., Catalysis Today, (2018), https: / / dol.org / 1-.1016 / j.cattod.2-18.08.009, it was shown that 4-propylphenol (a model feed of phenol derived from biomass lignin) could be transalkylated with benzene over H-beta, HZSM-5, and HMOR zeolites in a batch reactor. They found that HZSM-5 produced higher amounts of transalkylation products (phenol and propylbenzene) than H-beta and HMOR zeolites.

[0009]

[0013] US2020 / 0031741 describes a process and apparatus for transalkylating cresols from coal-derived liquids with toluene and / or benzene to phenols and aromatic / alkylbenzenes in the presence of a transalkylation catalyst (homogeneous or heterogeneous acid catalyst). It also describes transalkylating xylenols with benzene to make phenols and aromatic / alkylbenzenes in the presence of a transalkylation catalyst.

[0010]

[0014] However, the supplies of these references were limited (i.e., single compounds) and did not contain a wide range of alkylphenols. Low and medium temperature coal tar, cresylic acid, and crude phenol mixtures are complex mixtures of alkylphenols, containing higher percentages of dimethylphenols (e.g., 3.0-34.5 wt%), methylethylphenols (e.g., 0-3.0 wt%), and ethylphenols (e.g., 2.0-38.5 wt%) than propylphenols (e.g., 0-1%). The methyl and ethyl groups of alkylphenols are much more difficult to remove than the propyl groups.

[0011]

[0015] Coal-derived liquid streams from coal-derived feed streams contain a complex mixture of alkylphenols including one or more of methylphenols (cresols), ethylphenols, dimethylphenols (xylenols), propylphenols, butylphenols, methylethylphenols, etc., as well as heavier alkylphenols (e.g., indanol and naphthol). Catalysts comprising 3-dimensional 12-ring zeolites with a combination of smaller and larger pores have been found to increase the conversion of these complex mixtures of alkylphenols to phenols, cresols, and alkylbenzenes as compared to catalysts comprised of HZSM-5 zeolites.

[0012]

[0016] One suitable zeolite containing 3-dimensional 12-membered rings with a combination of smaller and larger pores is H-beta zeolite. Catalysts made with these zeolites increase the conversion of the complex mixture of alkylphenols described above to phenol, cresol, and alkylbenzenes compared to catalysts made of HZSM-5 zeolite. Catalysts containing H-beta zeolite are very stable during the transalkylation process, with the conversion of alkylphenols to phenol, cresol, and alkylbenzene decreasing by less than about 5% over 25 hours. As a result, catalysts containing H-beta zeolite can be successfully used to convert low and medium temperature coal tar, cresylic acid, or crude phenol mixtures to phenol, cresol, and aromatics such as benzene and xylene.

[0013]

[0017] Any suitable H-beta zeolite may be used. H-beta zeolite is a three-dimensional zeolite with 12-ring channels and a combination of large and small pores. The larger pores have a diameter of 6.6×6.7 (Å) and the small pores have a diameter of 5.6×5.6 (Å) (www.iza-structure.org / databases / ). The aluminum in the zeolite framework structure may be partially or completely replaced with other metals, such as, but not limited to, Fe, Ga, B, Ti, Sn, Zr, and combinations thereof. H-beta zeolite may have a silica / metal oxide molar ratio of 1 to 200, or 200 or less, or 150 or less, or 100 or less, or 80 or less, or 60 or less, or 50 or less, or 40 or less, or 30 or less, or 25 or less. When the metal oxide is alumina, this is commonly referred to as SAR (Silica / Alumina (SiO2 / Al2O3) Ratio). When aluminum in the framework structure is partially replaced by another metal, the amount of metal oxide in the silica / metal oxide ratio is the total amount of metal oxide (i.e., the amount of alumina + the amount of other metal oxide). H-beta zeolite is available from many companies, including, but not limited to, Zeolyst International, Clariant Ltd, and TOSOH Corporation. In Table 1, some properties of H-beta zeolite are compared with other common zeolites.

[0014]

[0018] Of the H-beta zeolites tested, the catalyst containing H-beta SAR25 zeolite was found to be the best catalyst for the transalkylation of ethylphenol and methylphenol with toluene, and for the transalkylation of 2,6-xylenol with toluene.

[0015]

[0019] Catalysts containing H-beta zeolite have product selectivities for phenol, cresols, and alkylbenzenes of 70% or more, or 75% or more, or 80% or more, or 85% or more, or 90% or more, or 95% or more. Catalysts containing H-beta zeolite have 4-ethylphenol conversions of 60% or more, or 65% or more, or 70% or more, or 75% or more, or 80% or more. Catalysts containing H-beta zeolite have 2,6-xylenol conversions of 20% or more, or 30% or more, or 40% or more.

[0016]

[0020] Catalysts comprising H-beta zeolite have phenol, cresol, and alkylbenzene productivity of 500 g / Kg catalyst / hour or more, or 750 g / Kg catalyst / hour or more, or 1000 g / Kg catalyst / hour or more, or 1250 g / Kg catalyst / hour or more, or 1300 g / Kg catalyst / hour or more, or 1500 g / Kg catalyst / hour or more, or 1750 g / Kg catalyst / hour or more, or 2000 g / Kg catalyst / hour or more.

[0017]

number

[0018]

[0021] The catalyst composition can be modified to improve catalyst stability and selectivity to desired products with minimal side reactions. For example, other zeolites (such as, but not limited to, HZSM-5, HY, HMOR, and HMCM-22, among others) can be mixed with H-Beta to adjust activity and product selectivity. In addition, the catalyst composition can include promoters, typically, but not limited to, one or more of transition metals from Groups IB-VIII, alkali metals from Group IA, alkaline earth metals from Group IIA, rare earth metals from the lanthanide series, metal oxides, metal sulfides, metal nitrides, metal phosphides, and combinations thereof. The catalyst can also be combined with porous inorganic support materials, such as alumina, silica, zirconia, titania, and combinations thereof.

[0019]

[0022] The catalyst typically comprises about 50% by weight or more, or about 60% by weight or more, or about 70% by weight or more, or about 75% by weight or more, or about 80% by weight or more, or about 85% by weight or more, or about 90% by weight or more, or about 95% by weight or more, or about 50% to 100%, or about 50% to about 99%, or about 50% to about 97%, or about 50% to about 95% H Beta zeolite.

[0020]

[0023] The catalyst may comprise less than about 40% by weight, or less than about 35% by weight, or less than about 30% by weight, or less than about 25% by weight, or less than about 20% by weight, or less than about 15% by weight, or less than about 10% by weight, or less than about 5% by weight, or less than about 3% by weight, or less than about 1% by weight of HZSM-5 catalyst.

[0021]

[0024] The catalyst is capable of efficiently and inexpensively transalkylating alkylphenols such as methylphenols (cresols), ethylphenols, dimethylphenols (xylenols), propylphenols, butylphenols, and methylethylphenols, as well as complex mixtures thereof, such as coal-derived liquid streams.

[0022]

[0025] The transalkylation process may be carried out in any suitable reactor type, such as, but not limited to, a fixed bed reactor, a moving bed reactor, an ebullated bed reactor, a fluidized bed reactor, a continuous catalyst regeneration (CCR) reactor, a semi-regenerative reactor, a batch reactor, a continuous stirred tank (CSTR) reactor, and a slurry bed reactor, or a combination thereof.

[0023]

[0026] Any suitable transalkylation reaction conditions may be used. The transalkylation reaction conditions will depend on the particular type of reactor used, as is known in the art. For example, in a fixed bed reactor, the transalkylation reaction conditions may be a temperature in the range of about 50° C. to about 600° C., a pressure in the range of about 0 to about 15 MPa, or a reaction time of about 0.1 to about 30 hours. -1 The liquid weight hourly space velocity may include at least one of the following ranges: 1. The liquid weight hourly space velocity may include at least one of the following ranges: 2. The liquid weight hourly space velocity may include at least one of the following ranges: 3. The liquid weight hourly space velocity may include at least one of the following ranges: 4. The liquid weight hourly space velocity may include at least one of the following ranges: 5. The liquid weight hourly space velocity may include at least one of the following ranges: 6. The liquid weight hourly space velocity may include at least one of the following ranges:

[0024]

[0027] One aspect of the invention is a process for transalkylation. In one embodiment, the process comprises transalkylating a coal-derived liquid stream comprising alkylphenols in a transalkylation reaction zone under transalkylation conditions in the presence of a co-reactant and a transalkylation catalyst comprising a three-dimensional 12-ring zeolite having a combination of small and large pores to produce a transalkylation effluent stream comprising one or more of phenols, cresols, and alkylbenzenes, where the conversion of alkylphenols to phenols, cresols, and alkylbenzenes is increased compared to a catalyst consisting of HZSM-5 zeolite.

[0025]

[0028] In some embodiments, the zeolite comprises greater than or equal to about 50% by weight H-Beta.

[0029] In some embodiments, the silica / metal oxide molar ratio of the zeolite is 80 or less.

[0026]

[0030] In some embodiments, the transalkylation catalyst further comprises up to about 40 wt.% HZSM-5 zeolite.

[0031] In some embodiments, the transalkylation catalyst comprises about 50% or more H-beta zeolite and 1-40% HZSM-5 zeolite, and the process provides increased productivity of phenol or cresol, or both, compared to a transalkylation catalyst consisting of HZSM-5 zeolite.

[0027]

[0032] In some embodiments, the aluminum in the zeolite framework structure is substituted with at least one of Fe, Ga, B, Ti, Sn, Zr, and combinations thereof.

[0028]

[0033] In some embodiments, the zeolite further comprises a promoter comprising one or more of a transition metal, an alkali metal, an alkaline earth metal, and a rare earth metal, a metal oxide, a metal sulfide, a metal nitride, a metal phosphide, and combinations thereof.

[0029]

[0034] In some embodiments, the catalyst further comprises a support comprising alumina, silica, zirconia, titania, or a combination thereof.

[0035] In some embodiments, the coal-derived liquid stream comprises a mixture of alkylphenols comprising two or more of methylphenol, ethylphenol, dimethylphenol, butylphenol, methylethylphenol, indanol, and naphthol, and optionally further comprising propylphenol.

[0030]

[0036] In some embodiments, the co-reactant may be a co-reactant such as benzene, toluene, or a combination thereof.

[0037] In some embodiments, the step of transalkylating the coal-derived liquid stream is carried out in the presence of hydrogen, nitrogen, or a combination thereof.

[0031]

[0038] In some embodiments, the transalkylation reaction zone comprises a fixed bed reactor, a moving bed reactor, an ebullated bed reactor, a fluidized bed reactor, a continuous catalyst regeneration (CCR) reactor, a semi-regenerative reactor, a batch reactor, a continuous stirred tank (CSTR) reactor, a slurry reactor, or a combination thereof.

[0032]

[0039] In some embodiments, the productivity of phenol, cresol, and alkylbenzene is 1300 g / Kg catalyst / hour or greater.

[0040] In some embodiments, the selectivity for phenol, cresols, and alkylbenzenes is about 70% or greater.

[0033]

[0041] In some embodiments, the coal-derived liquid stream comprises a low temperature coal tar stream, a medium temperature coal tar stream, a high temperature coal tar stream, a cresylic acid stream, or a crude phenol mixture.

[0042] In some embodiments, the method further comprises separating the transalkylation effluent into a phenol product stream comprising phenol and an alkylbenzene stream comprising alkylbenzene.

[0034]

[0043] In some embodiments, the method further includes separating the alkylbenzene stream into at least a recycle co-reactant stream, such as one or more of benzene or toluene, and recycling the recycle co-reactant stream to the transalkylation zone, the recycle stream comprising at least a portion of the co-reactants.

[0035]

[0044] In some embodiments, the step of separating the alkylbenzene stream into at least a recycle co-reactant stream includes separating the alkylbenzene stream into at least a recycle co-reactant stream and a mixed xylene stream comprising para-xylene, ortho-xylene, and meta-xylene, and recovering one or more of para-xylene, ortho-xylene, or meta-xylene from the mixed xylene stream.

[0036]

[0045] In some embodiments, the step of separating the transalkylation effluent into a product stream and an alkylbenzene stream comprises separating the transalkylation effluent into a phenol product stream, an alkylbenzene stream, and a cresol product stream comprising cresol, and further comprises recovering the cresol product stream.

[0037]

[0046] In some embodiments, the transalkylation effluent further comprises unreacted alkylphenol, and the step of separating the transalkylation effluent into a product stream and an alkylbenzene stream comprises separating the transalkylation effluent into a phenol product stream, an alkylbenzene stream, and an unreacted alkylphenol stream comprising unreacted alkylphenol, and further comprises recycling the unreacted alkylphenol stream to the transalkylation reaction zone.

[0038]

[0047] In some embodiments, the method further includes providing a coal-derived feed stream comprising phenol and a coal-derived liquid stream, and prior to transalkylating the coal-derived liquid stream, separating the coal-derived feed stream into at least a phenol stream comprising phenol and a coal-derived liquid stream, and recovering the phenol stream.

[0039]

[0048] In some embodiments, the method further includes providing a coal-derived feed stream comprising phenol and a coal-derived liquid stream, and prior to transalkylating the coal-derived liquid stream, separating the coal-derived feed stream into at least a phenol-cresol stream comprising phenol and cresol and a coal-derived liquid stream, and recovering the phenol-cresol stream.

[0049] EXAMPLES

[0040]

[0050] The following commercially available catalysts were evaluated:

[0041] [Table 1]

[0042]

[0051] Example 1

[0052] Several commercially available zeolites were evaluated for the transalkylation of 4-ethylphenol (4-EP) with toluene to form phenol and ethyltoluene.

[0043]

[0053] The reaction conditions were: temperature 400°C, pressure 1350 psig, WHSV 2.3 hours. -1 The experiment involved the use of 1.25 g catalyst, toluene:feed of 11 mol / mol, and an isothermal fixed bed reactor set at a N2 feed rate of 25 mL / min. The catalyst was pretreated in N2, heated to 200°C (3°C / min) and held at 200°C for 2 hours, then heated to 450°C (5°C / min) and held for 3 hours, then cooled to 400°C.

[0044]

[0054] Table 2 and Figure 1 show the conversion results for 4-ethylphenol. Conversions and selectivities were obtained after 30 hours TOS (time on stream) for most runs or 35 hours TOS for HBeta SAR25, HBeta SAR150, and HZSM-5 SAR80. Product selectivities are based on the composition of carbon products excluding toluene and 4-ethylphenol. BEX refers to benzene, ethylbenzene, and xylenes.

[0045]

[0055] As shown in Figure 1, catalysts containing H-beta SAR25 and H-beta SAR38 zeolites outperformed catalysts containing HZSM-5 SAR30 and HZSM-5 SAR80 zeolites. Catalysts containing H-beta SAR150 zeolites outperformed HZSM-5 SAR30 and HZSM-5 SAR80 zeolites after 20 hours of TOS. In addition, catalysts containing a combination of 80% H-beta SAR25 zeolite and 20% HZSM-5 SAR80 zeolite also outperformed catalysts containing HZSM-5 SAR80 zeolite alone.

[0046]

[0056] The catalyst containing HBeta SAR25 was the best catalyst for the reaction of 4-EP with toluene with a conversion of over 81% and a product selectivity of over 69% for the desired phenol and ethyltoluene products. The catalyst containing HBeta SAR38 had the highest phenol + cresol productivity of 1180 g / kg cat / hr and phenol + cresol + alkylbenzene (BEX and ethyltoluene) productivity of 3056 g / kg cat / hr.

[0047]

[0057] The HBeta SAR25 containing catalyst only lost 2% conversion over 30 hours of TOS, demonstrating catalytic stability.

[0058] Another favorable pathway (toluene disproportionation) converts toluene to benzene, ethylbenzene, and xylenes (BEX). The catalyst containing HBeta SAR25 had a product selectivity of 12.6% for the conversion of toluene to BEX.

[0048]

[0059] The catalyst containing a mixture of 80% HBeta SAR25 and 20% HZSM-5 SAR80 had a slightly lower conversion of about 77% compared to 81% for the catalyst containing all HBeta SAR25, but the selectivity of the desired products (phenol + ethyltoluene) improved from 69% to over 72%, while the amount of other products decreased from 10.0% to 7.7%.

[0049]

[0060] Example 2

[0061] Several commercial zeolites were evaluated for the transalkylation of 2,6-xylenol with toluene to form phenol, cresol, benzene, and xylene along with other alkylbenzenes. The reaction conditions were: temperature 400°C, pressure 1350 psig, WHSV 2.3 h. -1 The experiment involved the use of 1.25 g catalyst, toluene:feed of 10 mol / mol, and an isothermal fixed bed reactor set at a N2 feed rate of 25 mL / min. The catalyst was pretreated in N2, heated to 200°C (3°C / min) and held at 200°C for 2 hours, then heated to 450°C (5°C / min) and held for 3 hours, then cooled to 400°C.

[0050]

[0062] Conversions and selectivities were obtained at a TOS of 35 h.

[0063] As shown in Table 3 and FIG. 2, HBeta SAR25 and HBeta SAR150 zeolites outperformed the HZSM-5 SAR80 zeolite.

[0051]

[0064] Again, HBeta SAR150 was the best catalyst in this reaction, with conversions over 95% and selectivities over 55% for the desired cresol and xylene products, as shown in Table 2. HBeta SAR150 had the highest phenol + cresol productivity of 931 g / kg cat / hr and phenol + cresol + alkylbenzene productivity of 2791 g / kg cat / hr. Furthermore, the conversion only decreased by 1% over the 25 hour TOS. HBeta SAR25 performed nearly as well as HBeta SAR150, with conversions over 95% and selectivities over 52% for the desired cresol and xylene products.

[0052]

[0065] The conversion of 2,6-xylenol was higher compared to 4-EP, but the methyl group of 2,6-xylenol was found to be more difficult to remove than the ethyl group of 4-EP. At Hbeta SAR25, the transalkylation of 4-EP only showed a selectivity to isomerization products (other ethyl phenols) of 5.4%, while the transalkylation of xylenol had a much higher selectivity to isomerization products (other xylenols) of 23.8%.

[0053]

[0066] Example 3

[0067] Commercially available zeolites were evaluated for the transalkylation of 4-ethylphenol (4-EP) with toluene to form phenol and ethyltoluene. Conditions were the same as in Example 1, except that the gas feed was a mixture of N2 at a feed rate of 12.5 mL / min and H2 at a feed rate of 12.5 mL / min.

[0054]

[0068] Conversions and selectivities were obtained at a TOS of 30 h.

[0069] As shown in Table 4 and Figure 3, with the addition of H2 co-feed, the conversion of ethylphenol for HZSM-5 SAR80 increased to 78.8% compared to 77.9% for HBeta SAR25. The productivity of phenol and cresol was also higher at 1050 g / kg cat / hr, but the productivity of phenol + cresol + alkylbenzene, 2349 g / kg cat / hr, was lower than 2387 g / kg cat / hr for HBeta SAR25.

[0055]

[0070] Example 4

[0071] Several commercial zeolites were evaluated for the transalkylation of cresylic acid (SASOL, CA68) with toluene to form phenol, cresol, ethyltoluene, and xylene along with benzene and other alkylbenzenes. The composition of the cresylic acid was 25 wt% cresol, 34.5 wt% xylenol, 38.5 wt% ethylphenol, and 2.0 wt% other compounds (measured). The reaction conditions were: temperature 400°C, pressure 1350 psig, WHSV 2.3 hours. -1 The experiment involved the use of an isothermal fixed bed reactor set at 1.25 g catalyst, 8.2 g / g toluene:cresylic acid, a N2 feed rate of 12.5 mL / min, and a H2 feed rate of 12.5 mL / min. The catalyst was pretreated in N2, heated to 200°C (3°C / min) and held at 200°C for 2 hours, then heated to 450°C (5°C / min) and held for 3 hours, then cooled to 400°C.

[0056]

[0072] Conversion and selectivity were obtained at 30 h TOS, except for HY SAR at 25 h TOS. Negative selectivity means that cresol was destroyed during the process.

[0057]

[0073] As shown in Table 5 and Figures 4A and 4B, HBeta SAR25 was found to be better for converting both ethylphenol and xylenol in cresylic acid compared to the other zeolites tested. HZSM-5 SAR30 was found to be a better catalyst than HBeta SAR25 for the conversion of ethylphenol, with 79% conversion compared to 69% for HBeta SAR25. However, for the conversion of xylenol, HBeta SAR25 was the better catalyst with 49% conversion compared to 26% for HZSM-5 SAR30. HZSM-5 SAR30 was found to have the highest phenol + cresol productivity of 472 g / kg cat / hr, slightly higher than HBeta SAR25's 468 g / kg cat / hr. However, HBeta SAR25 had the highest phenol + cresol + alkylbenzene productivity of 1235 g / kg cat / hr.

[0058]

[0074] All catalysts had selectivities to the desired products (phenol, cresol, ethyltoluene, and BEX) greater than 90%, with selectivities to other products (diethylphenol, gas, and unknown liquid) less than 10%.

[0059]

[0075] Next, HBeta SAR25 (80%) was mixed with several other catalysts (20%) and the results are shown in Figures 5A and 5B. With the addition of 20% HZSM-5 SAR30, the conversion of ethylphenol increased to 81%, while the conversion of xylenol was slightly lower than with pure HBeta SAR25, at 45.5% conversion. The amount of unknown liquid was also reduced to 3.0%, compared to 5.3% with pure HBeta SAR25. This catalyst mixture was also found to have the highest phenol + cresol productivity of 509 g / kg cat / hr and phenol + cresol + alkylbenzene productivity of 1368 g / kg cat / hr.

[0060] [Table 2]

[0061] [Table 3]

[0062] [Table 4]

[0063] [Table 5]

[0064] [Table 6]

[0065]

[0076] As used herein, the term "zone" may refer to an area that includes one or more equipment and / or one or more subzones. Equipment may include one or more reactors or reaction vessels, heaters, exchangers, pipes, pumps, compressors, and controllers. In addition, equipment, such as reactors, dryers, or vessels, may further include one or more zones or subzones.

[0066]

[0077] As used herein, the term "about" means within 10%, or within 5%, or within 1% of a value.

[0067]

[0078] In the foregoing detailed description of the present invention, at least one exemplary embodiment has been presented, but it should be understood that a vast number of variations exist. It should also be understood that the exemplary embodiment or embodiments are merely examples, and are in no way intended to limit the scope, applicability, or configuration of the present invention. Rather, the foregoing detailed description will provide those skilled in the art with a convenient guide for implementing the exemplary embodiments of the present invention. It should be understood that various changes may be made in the function and arrangement of elements described in the exemplary embodiments without departing from the scope of the present invention as set forth in the appended claims. The present invention includes the following aspects. [1] 1. A process for transalkylation comprising the steps of: 1. A method comprising: transalkylating a coal-derived liquid stream comprising alkylphenols in a transalkylation reaction zone under transalkylation conditions in the presence of a co-reactant and a transalkylation catalyst comprising a three-dimensional 12-ring zeolite having a combination of small and large pores to produce a transalkylation effluent stream comprising one or more of phenols, cresols, and alkylbenzenes, wherein the conversion of alkylphenols to phenols, cresols, and alkylbenzenes is increased as compared to a catalyst consisting of HZSM-5 zeolite. [2] 2. The method of claim 1, wherein the zeolite comprises about 50% by weight or more of H-beta. [3] 3. The method according to claim 1 or 2, wherein the zeolite has a silica / metal oxide molar ratio of 80 or less. [4] 4. The process of any one of 1 to 3, wherein the transalkylation catalyst further comprises up to about 40 wt.% HZSM-5 zeolite. [5] 5. The process of any one of claims 1 to 4, wherein the transalkylation catalyst comprises about 50% or more H-beta zeolite and 1-40% HZSM-5 zeolite, and the process provides increased productivity of phenol or cresol or both compared to a transalkylation catalyst consisting of HZSM-5 zeolite. [6] 6. The method of any one of 1 to 5, wherein aluminum in the framework structure of the zeolite is substituted with at least one of Fe, Ga, B, Ti, Sn, Zr, and combinations thereof. [7] 7. The method of any one of 1 to 6, wherein the zeolite further comprises a promoter comprising one or more of a transition metal, an alkali metal, an alkaline earth metal, and a rare earth metal, a metal oxide, a metal sulfide, a metal nitride, a metal phosphide, and combinations thereof. [8] 8. The method of any one of 1 to 7, wherein the catalyst further comprises a support comprising alumina, silica, zirconia, titania, or a combination thereof. [9] 9. The method of any one of claims 1 to 8, wherein the coal-derived liquid stream comprises a mixture of alkylphenols comprising two or more of methylphenol, ethylphenol, dimethylphenol, butylphenol, methylethylphenol, indanol, and naphthol, and optionally further comprising propylphenol.

[10] 10. The method of any one of 1 to 9, wherein the co-reactant comprises benzene, toluene, or a combination thereof.

[11] 11. The method of any one of 1 to 10, wherein the step of transalkylating the coal-derived liquid stream is carried out in the presence of hydrogen, nitrogen, or a combination thereof.

[12] 12. The process of any one of claims 1 to 11, wherein the transalkylation reaction zone comprises a fixed bed reactor, a moving bed reactor, an ebullated bed reactor, a fluidized bed reactor, a continuous catalyst regeneration (CCR) reactor, a semi-regenerative reactor, a batch reactor, a continuous stirred tank (CSTR) reactor, a slurry reactor, or a combination thereof.

[13] 13. The process of any one of 1 to 12, wherein the selectivity for phenol, cresol, and alkylbenzene is about 70% or greater.

[14] 14. The method of any one of claims 1 to 13, wherein the coal-derived liquid stream comprises a low temperature coal tar stream, a medium temperature coal tar stream, a high temperature coal tar stream, a cresylic acid stream, or a portion of a coal-derived feed stream comprising a crude phenol mixture.

[15] separating the transalkylation effluent into a phenol product stream comprising phenol and an alkylbenzene stream comprising alkylbenzenes. 15. The method of any one of 1 to 14, further comprising:

[16] separating the alkylbenzene stream into at least a recycle co-reactant stream comprising one or more of benzene or toluene; recycling the recycled co-reactant stream to the transalkylation zone. 16. The method of claim 15, further comprising:

[17] separating the alkylbenzene stream into at least a recycle co-reactant stream, separating the alkylbenzene stream into at least a recycle co-reactant stream and a mixed xylenes stream comprising para-xylene, ortho-xylene, and meta-xylene; Recovering one or more of para-xylene, ortho-xylene, or meta-xylene from the mixed xylene stream; 17. The method according to claim 16, comprising:

[18] separating the transalkylation effluent into a phenol product stream and an alkylbenzene stream, separating the transalkylation effluent into a phenol product stream, an alkylbenzene stream, and a cresol product stream comprising cresol; 16. The method of claim 15, further comprising recovering a cresol product stream.

[19] the transalkylation effluent further comprising unreacted alkylphenol, and separating the transalkylation effluent into a product stream and an alkylbenzene stream comprises: separating the transalkylation effluent into a phenol product stream, an alkylbenzene stream, and an unreacted alkylphenol stream comprising unreacted alkylphenol; 19. The process of any one of 1 to 18, further comprising recycling the unreacted alkylphenol stream to the transalkylation reaction zone.

[20] providing a coal-derived feed stream comprising phenol and a coal-derived liquid stream; prior to transalkylating the coal-derived liquid stream, separating the coal-derived feed stream into at least a phenol stream comprising phenol and a coal-derived liquid stream; recovering the phenol stream. 20. The method of any one of 1 to 19, further comprising:

[21] providing a coal-derived feed stream comprising phenol and a coal-derived liquid stream; prior to transalkylating the coal-derived liquid stream, separating the coal-derived feed stream into at least a phenol-cresol stream comprising phenol and cresol and a coal-derived liquid stream; recovering the phenol-cresol stream; 20. The method of any one of 1 to 19, further comprising:

Claims

1. 1. A process for transalkylation comprising the steps of: transalkylating a coal-derived liquid stream comprising alkylphenols in a transalkylation reaction zone under transalkylation conditions in the presence of a co-reactant and a transalkylation catalyst comprising a three-dimensional 12-ring zeolite having a combination of small and large pores and a second zeolite to produce a transalkylation effluent stream comprising one or more of phenols, cresols, and alkylbenzenes; The three-dimensional 12-ring zeolite is H-beta zeolite; the second zeolite is a HZSM-5 SAR30 zeolite; the transalkylation catalyst comprises at least 50 wt. % H-beta zeolite and 1-40 wt. % HZSM-5 SAR30 zeolite; The process wherein the transalkylation conditions include at least one of a temperature in the range of 50° C. to 600° C., a pressure in the range of 0 to 15 MPa, or a liquid weight hourly space velocity in the range of 0.1 to 30 hr −1 .

2. The method of claim 1, wherein the aluminum in the framework structure of the three-dimensional 12-membered ring zeolite is substituted with at least one of Fe, Ga, B, Ti, Sn, Zr, and combinations thereof.

3. The method of any one of claims 1 to 2, wherein the three-dimensional 12-membered ring zeolite further comprises a co-catalyst comprising one or more of a transition metal, an alkali metal, an alkaline earth metal, and a rare earth metal, a metal oxide, a metal sulfide, a metal nitride, a metal phosphide, and combinations thereof.

4. 4. The method of any one of claims 1 to 3, wherein the catalyst further comprises a support comprising alumina, silica, zirconia, titania, or a combination thereof.

5. 5. The method of any one of claims 1 to 4, wherein the coal-derived liquid stream comprises a mixture of alkylphenols comprising two or more of methylphenol, ethylphenol, dimethylphenol, butylphenol, methylethylphenol, indanol, and naphthol, and optionally further comprising propylphenol.

6. 6. The method of claim 1, wherein the co-reactant comprises benzene, toluene, or a combination thereof.

7. 7. The method of any one of claims 1 to 6, wherein the step of transalkylating the coal-derived liquid stream is carried out in the presence of hydrogen, nitrogen, or a combination thereof.

8. 8. The process of any one of claims 1 to 7, wherein the transalkylation reaction zone comprises a fixed bed reactor, a moving bed reactor, an ebullated bed reactor, a fluidized bed reactor, a continuous catalyst regeneration (CCR) reactor, a semi-regenerative reactor, a batch reactor, a continuous stirred tank (CSTR) reactor, a slurry reactor, or a combination thereof.

9. 9. The process according to any one of claims 1 to 8, wherein the selectivity for phenol, cresol, and alkylbenzene is 70% or more.

10. 10. The method of any one of claims 1 to 9, wherein the coal-derived liquid stream comprises a low temperature coal tar stream, a medium temperature coal tar stream, a high temperature coal tar stream, a cresylic acid stream, or a portion of a coal-derived feed stream comprising a crude phenol mixture.

11. separating the transalkylation effluent into a phenol product stream comprising phenol and an alkylbenzene stream comprising alkylbenzenes. The method of claim 1 , further comprising:

12. separating the alkylbenzene stream into a recycle co-reactant stream comprising at least one or more of benzene or toluene; recycling the recycled co-reactant stream to the transalkylation zone.

12. The method of claim 11, further comprising:

13. separating the alkylbenzene stream into at least a recycle co-reactant stream, separating the alkylbenzene stream into at least a recycle co-reactant stream and a mixed xylenes stream comprising para-xylene, ortho-xylene, and meta-xylene; Recovering one or more of para-xylene, ortho-xylene, or meta-xylene from the mixed xylene stream; The method of claim 12, comprising:

14. separating the transalkylation effluent into a phenol product stream and an alkylbenzene stream, separating the transalkylation effluent into a phenol product stream, an alkylbenzene stream, and a cresol product stream comprising cresol; 12. The method of claim 11 further comprising recovering a cresol product stream.

15. the transalkylation effluent further comprising unreacted alkylphenol, and separating the transalkylation effluent into a product stream and an alkylbenzene stream comprises: separating the transalkylation effluent into a phenol product stream, an alkylbenzene stream, and an unreacted alkylphenol stream comprising unreacted alkylphenol; 15. The process of any one of claims 1 to 14, further comprising recycling the unreacted alkylphenol stream to the transalkylation reaction zone.

16. providing a coal-derived feed stream comprising phenol and a coal-derived liquid stream; prior to transalkylating the coal-derived liquid stream, separating the coal-derived feed stream into at least a phenol stream comprising phenol and a coal-derived liquid stream; recovering the phenol stream.

16. The method of claim 1, further comprising:

17. providing a coal-derived feed stream comprising phenol and a coal-derived liquid stream; prior to transalkylating the coal-derived liquid stream, separating the coal-derived feed stream into at least a phenol-cresol stream comprising phenol and cresol and a coal-derived liquid stream; recovering the phenol-cresol stream; 16. The method of claim 1, further comprising:

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