PREPARATION METHOD FOR METHYLPHENOL AND HOMOLOGUE

Abstract

A preparation method for methylphenol and homologue. Under the conditions of reaction temperature of 150-350 C. and reaction pressure of 1-50 atm, a mixed material of methanol, ethanol and acetone is fed into a reactor containing a catalyst by a carrier gas to produce methylphenol through coupling-aromatization reaction. The method provides a reaction path for directly producing methylphenol and homologue from low carbon micromolecular alcohol and ketone through coupling-aromatization reaction, the maximum selectivity of total cresol is 34.0%, and the selectivity of 2,3,6-trimethylphenol is up to 7.1%. The by-product hydrogen of the reaction path can be used as a chemical material. Other by-products such as high carbon alcohol and ketone whose melting and boiling points are quite different from those of methylphenol and which are easy to be separated by rectification can be used as fuel additives to partially replace petroleum-based products.

Claims

1. A preparation method for methylphenol and homologue, comprising the following steps: under the conditions of reaction temperature of 150-350 C. and reaction pressure of 1-50 atm, a mixed material of methanol, ethanol and acetone is fed into a reactor containing a catalyst by a carrier gas at the total flow of the reaction gas of 20-200 mL/min to produce methylphenol through coupling-aromatization reaction.

2. The preparation method according to claim 1, wherein the ranges of partial pressures of the reactants methanol, ethanol and acetone are respectively 0.1-10 kPa, and the weight hourly space velocity of the reaction is 0.01-3 h.sup.1.

3. The preparation method according to claim 2, wherein the ratio of partial pressures of methanol, ethanol and acetone is (0.5-40):(0.5-40):1, the total flow of the reaction gas is 30 mL/min is 30 mL/min, and the weight hourly space velocity of the reaction is 0.2-1.5 h.sup.1.

4. The preparation method according to claim 1, wherein the carrier gas is nitrogen, argon or helium.

5. The preparation method according to claim 1, wherein the catalyst is a mixture of a hydroxyphosphate catalyst and/or a hydroxyphosphate catalyst modified by transition metal.

6. The preparation method according to claim 5, wherein the chemical formula of the hydroxyphosphate is A.sub.xB.sub.yC.sub.zD.sub.mE.sub.n(OH).sub.2(PO.sub.4).sub.6, x+y+z+m+n=9-10, 9-10x,y,z,m,n0, A, B, C, D and E are the same or different, and are selected from one or a combination of more than one of Mg, Ca, Sr, Ba and Pb, and the hydroxyphosphate is one or a mechanical mixture of more than one.

7. The preparation method according to claim 6, wherein the hydroxyphosphate is Ca.sub.10(OH).sub.2(PO.sub.4).sub.6.

8. The preparation method according to claim 5, wherein the hydroxyphosphate catalyst modified by transition metal comprises components by weight percent; the transition metal comprises non-noble metal and/or noble metal; the non-noble metal is selected from one or a combination of more than one of Co, Ni, Cu, Zn and Y; the noble metal is selected from one or a combination of more than one of Ag, Pt and Ir; the transition metal is in an oxidation state or metallic state; and the transition metal uses nitrate, chloride, levulinate, sulfate or acetate of the metal as a precursor, the concentration of a precursor solution is 0.05 g/mL-0.75 g/mL, and the modification amount of the transition metal is 0.01-50 wt % of the weight of hydroxyphosphate.

9. The preparation method according to claim 8, wherein the transition metal is Ag and Cu, and the modification amount is 0.1-10 wt % of the hydroxyphosphate.

10. The preparation method according to claim 5, wherein the hydroxyphosphate catalyst modified by transition metal is reduced for 1-5 h at 350-750 C. in hydrogen atmosphere before reaction, and the concentration of the hydrogen atmosphere is one of 5-30 vol % H.sub.2/N.sub.2, 5-30 vol % H.sub.2/He and 5-30 vol % H.sub.2/Ar.

Description

DESCRIPTION OF DRAWINGS

[0023] The FIGURE shows a reaction path for producing methylphenol by coupling of methanol, ethanol and acetone proposed in the present invention, and MPV reaction is Meerwein-Ponndorf-Verley hydrogenation reaction.

DETAILED DESCRIPTION

[0024] The present invention is described below in detail through some embodiments. However, the present invention is not limited to these embodiments.

[0025] Hydroxyphosphate is represented by HAP-M, wherein HAP indicates metal hydroxyphosphate, and M indicates metal which is one or several of Mg, Ca, Sr, Ba and Pb.

[0026] Hydroxyphosphate modified by metal is represented by an xMetal-HAP-M carrier, wherein Metal indicates loaded transition metal and is one or several of non-noble metal such as Co, Ni, Cu, Zn and Y and/or noble metal such as Pt, Ag and Ir, and x is the percentage of the Metal modification amount in the total weight of the catalyst multiplied by 100.

Embodiment 1

Preparation Process for HAP-Ca Catalyst:

[0027] (1) Ca(NO.sub.3).sub.2.Math.xH.sub.2O and (NH.sub.4).sub.2HPO.sub.4 are prepared into 0.5 mol/L and 0.3 mol/L aqueous solutions; [0028] (2) The two salt solutions are mixed according to the volume ratio of 1:1 at 25 C., the pH of the mixture is adjusted to 10 with ammonia, and the mixture is stirred and mixed with a magnetic stirrer for 2 h; [0029] (3) The mixture obtained by stirring in step (2) is kept reacting for 24 h in a 80 C. homogeneous reactor or hydrothermal device for 24 h; [0030] (4) The sediment obtained in step (3) is filtered, and dried at 100 C., and the obtained precursor is roasted in air atmosphere at 600 C. for 2 h to obtain the HAP-Ca catalyst which corresponds to No. 1 in Table 1; [0031] (5) Different HAP-Ms can be prepared by controlling the type of metal (one or several of Mg, Ca, Sr, Ba and Pb) in the nitrate solution in the same method as the above steps.

[0032] The preparation conditions and process of other catalysts are the same as those in embodiment 1. The corresponding relation between sample numbers and preparation conditions is shown in Table 1.

TABLE-US-00001 TABLE 1 Corresponding Relation between Sample Numbers and Preparation Conditions in Embodiment 1 Hydro- thermal Drying Roasting Tempera- Tempera- Tempera- No. Catalyst Metal Salt ture/ C. ture/ C. ture/ C. 1 HAP-Ca Calcium 80 100 600 nitrate 2 HAP-Mg Magnesium 80 100 600 nitrate 3 HAP-Sr Strontium 80 100 600 nitrate 4 HAP-Ba Barium 80 100 600 nitrate 5 HAP-Pb Lead nitrate 80 100 600 6 HAP-Ca/Sr Calcium 80 100 600 nitrate + strontium nitrate

Embodiment 2

Preparation Process for HAP-Ca Catalyst Modified by Ag Species:

[0033] (1) HAP-Ca is dried in a 120 C. airflow oven for 2 h to remove physical adsorbed water on the surface; [0034] (2) An AgNO.sub.3 aqueous solution with a mass concentration of 0.05 g/mL is prepared at 25 C., and the HAP-Ca obtained by drying in step (1) is treated with an incipient-wetness impregnation method and kept standing for 2 h; [0035] (3) The mixture obtained after standing in step (2) is dried in 50 C. air atmosphere for 10 h to obtain a catalyst precursor; [0036] (4) The catalyst precursor obtained in step (3) is roasted in air atmosphere at 350 C. for 2 h, and then reduced in 400 C. hydrogen atmosphere for 2 h (10 vol % H.sub.2/N.sub.2) to obtain an Ag-modified HAP-Ca catalyst which is denoted as 0.1 Ag-HAP-Ca catalyst and corresponds to No. 1 in Table 2. [0037] (5) The type and modification amount of the metal can be controlled by controlling the type, the concentration and the number of impregnations of the metal salt solution, and the preparation method is the same as the above steps.

[0038] The preparation conditions and process of other catalysts are the same as those in embodiment 2. The corresponding relation between sample numbers and preparation conditions is shown in Table 2.

TABLE-US-00002 TABLE 2 Corresponding Relation between Sample Numbers and Preparation Conditions in Embodiment 2 Metal/ Metal Concentration/ Reduction No. Catalyst wt % Carrier Salt Solvent g mL.sup.1 Temperature 1 0.1Ag-HAP-Ca 0.1 HAP-Ca Silver Water 0.05 400 nitrate 2 0.3Ag-HAP-Ca 0.3 HAP-Ca Silver Water 0.15 400 nitrate 3 0.5Ag-HAP-Ca 0.5 HAP-Ca Silver Water 0.25 400 nitrate 4 0.8Ag-HAP-Ca 0.8 HAP-Ca Silver Water 0.40 400 nitrate 5 1.6Ag-HAP-Ca 1.6 HAP-Ca Silver Water 0.75 400 nitrate 6 0.8Ag-HAP-Sr 0.8 HAP-Sr Silver Water 0.40 400 nitrate 7 0.8Ag-HAP-Mg 0.8 HAP-Mg Silver Water 0.40 400 nitrate 8 0.8Ag-HAP-Ba 0.8 HAP-Ba Silver Water 0.40 400 nitrate 9 0.8Ag-HAP-Pb 0.8 HAP-Pb Silver Water 0.40 400 nitrate 10 0.8Ag-HAP-Ca/Sr 0.8 HAP-Ca/Sr Silver Water 0.40 400 nitrate 11 0.5Co-HAP-Ca 0.5 HAP-Ca Cobalt Water 0.25 400 nitrate 12 0.5Ni-HAP-Ca 0.5 HAP-Ca Nickel Water 0.25 400 nitrate 13 0.5Zn-HAP-Ca 0.5 HAP-Ca Zinc Water 0.25 400 nitrate 14 0.5Cu-HAP-Ca 0.5 HAP-Ca Copper Water 0.25 400 nitrate 15 0.25Cu0.25Ag-HAP-Ca 0.5 HAP-Ca Copper Water 0.5 400 nitrate + silver nitrate 16 0.5Cu-HAP-Ca + 0.5 HAP-Ca Copper Water 0.5 400 0.5Ag-HAP-Ca nitrate + silver nitrate

Embodiment 3

Effect of Partial Pressures of Methanol, Ethanol and Acetone for HAP-Ca Catalyst on Selectivity of Methylphenol.

[0039] Methanol, ethanol and acetone as reactants are subjected to coupling-aromatization reaction in a fix bed reactor. Reaction conditions are as follows: the catalyst is filled in a fix bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300 C., the weight hourly space velocity is 1 h.sup.1, the total flow of the reaction gas is 30 mL/min, the total partial pressure of methanol and ethanol is 6 kPa, the partial pressure of acetone is 1 kPa, the ratio of the partial pressures of methanol, ethanol and acetone is (1-5):(1-5):1, and the partial pressures of the reactants are adjusted by adjusting the feed flow of methanol, ethanol and acetone. After the reaction is steady, the reaction materials and products are analyzed by on-line chromatogram. The conversion rates of methanol and ethanol and the selectivity of methylphenol at different partial pressures are shown in Table 3, and the selectivity of acetone is close to 100% which is not listed in Table 3.

TABLE-US-00003 TABLE 3 Effect of Relative Partial Pressures of Methanol and Ethanol on Selectivity of Methylphenol in Embodiment 3 Methyl- Methanol Ethanol phenol Methanol Ethanol Acetone/% Conversion Conversion Selec- (kPa) (kPa) (kPa) Rate/% Rate/% tivity/% 1 5 1 14.9 33.5 2.6 2 4 1 18.5 29.5 2.2 3 3 1 17.4 32.3 2.3 4 2 1 20.8 33.8 15.8 5 1 1 23.6 33.8 6.4

Embodiment 4

Effect of Relative Partial Pressure of Acetone for HAP-Ca Catalyst on Selectivity of Methylphenol.

[0040] Methanol, ethanol and acetone as reactants are subjected to coupling-aromatization reaction in a fix bed reactor. Reaction conditions are as follows: the catalyst is filled in a fix bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300 C., the weight hourly space velocity is 1 h.sup.1, the total flow of the reaction gas is 30 mL/min, the partial pressure of methanol is 4 kPa, the partial pressure of ethanol is 2 kPa, the partial pressure of acetone is adjusted between 0.33 kPa and 3 kPa and adjusted by changing the feed flow of acetone, and the ratio of the partial pressures of methanol, ethanol and acetone is (1.33-12.12):(0.67-6.06):1. The conversion rates of methanol and ethanol and the selectivity of methylphenol at different partial pressures of acetone are shown in Table 4. The selectivity of acetone is close to 100% which is not listed in Table 4.

TABLE-US-00004 TABLE 4 Effect of Relative Partial Pressure of Acetone on Selectivity of Methylphenol in Embodiment 4 Methyl- Methanol Ethanol phenol Methanol Ethanol Acetone Conversion Conversion Selec- (kPa) (kPa) (kPa) Rate/% Rate/% tivity/% 4 2 0.33 13.1 24.7 1.3 4 2 0.66 17.1 27.5 1.0 4 2 1 20.8 33.8 17.2 4 2 1.5 22.3 32.2 21.6 4 2 2 24.3 33.8 28.3 4 2 3 25.7 37.5 25.4

Embodiment 5

Catalytic Conversion Performance of xMetal-HAP-M Catalyst.

[0041] Methanol, ethanol and acetone as reactants are subjected to coupling-aromatization reaction in a fix bed reactor. Reaction conditions are as follows: the catalyst is filled in a fix bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300 C., the weight hourly space velocity is 1 h.sup.1, the total flow of the reaction gas is 30 mL/min, the partial pressure of methanol is 4 kPa, the partial pressure of ethanol is 2 kPa, the partial pressure of acetone is 1 kPa, and the ratio of the partial pressures of methanol, ethanol and acetone is 4:2:1. Different xMetal-HAP-M materials are used as catalysts for the reaction, and the preparation method for the xMetal-HAP-M catalyst is shown in embodiment 2. The conversion rates of methanol and ethanol and the selectivity of methylphenol for different catalysts are shown in Table 5. The selectivity of acetone is close to 100% which is not listed in Table 5.

TABLE-US-00005 TABLE 5 Catalysis Performance of Different xMetal- HAP-M Catalysts in Embodiment 5 Methyl- Methanol Ethanol phenol Conversion Conversion Selec- No. Catalyst Rate/% Rate/% tivity/% 1 0.1Ag-HAP-Ca 22.5 35.1 17.5 2 0.3Ag-HAP-Ca 25.0 37.1 23.4 3 0.5Ag-HAP-Ca 27.1 32.9 28.5 4 0.8Ag-HAP-Ca 33.9 27.9 34.0 5 1.6Ag-HAP-Ca 35.1 33.2 32.0 6 0.8Ag-HAP-Sr 22.3 32.2 21.6 7 0.8Ag-HAP-Mg 17.0 25.1 12.1 8 0.8Ag-HAP-Ba 19.7 23.3 13.2 9 0.8Ag-HAP-Pb 15.0 20.1 10.1 10 0.8Ag-HAP-Ca/Sr 14.0 24.7 15.1 11 0.5Co-HAP-Ca 21.0 27.0 3.0 12 0.5Ni-HAP-Ca 29.2 40.2 14.9 13 0.5Zn-HAP-Ca 21.6 30.5 15.6 14 0.5Cu-HAP-Ca 17.4 20.7 21.1 15 0.25Cu0.25Ag-HAP-Ca 20.3 33.7 26.5 16 0.5Cu-HAP-Ca + 21.2 32.5 27.6 0.5Ag-HAP-Ca

Reference Example 1

Product Distribution During Separate Feeding of Methanol, Ethanol and Acetone for HAP-Ca Catalyst.

[0042] Methanol, ethanol and acetone as reactants are subjected to catalytic reaction testing in a fix bed reactor. Reaction conditions are as follows: the catalyst is filled in a fix bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300 C., the weight hourly space velocity is 1 h.sup.1, the total flow of the reaction gas is 30 mL/min, and the partial pressures of ethanol, methanol and acetone are all 6 kPa. The product distribution during the reaction of different reactants is shown in Table 6.

TABLE-US-00006 TABLE 6 Selectivity of Products Corresponding to Different Reaction Substrates in Reference Example 1 Product Selectivity/% Temperature/ Conversion Dimethyl C.sub.6-12 Mesityl Trimethyl- Methyl Reactant C. Rate/% ether n-butanol alcohol oxide Isophorone benzene C.sub.10+ phenol Methanol 300 1.1 100 ~0 Ethanol 300 7.5 75.8 13.2 ~0 Acetone 300 75.2 5.5 12.3 13.5 67.5 ~0 Note: The C.sub.10+ product is a high molecular weight product of low polymerization of acetone.

[0043] As shown in Table 6, when raw materials are fed separately in the reaction, the product distribution of the three substrates is different, and the products do not contain methylphenol, which indicates that methylphenol cannot be obtained by separate feeding at low temperature.

Reference Example 2

Effect of Mixed Feeding of Methanol, Ethanol and Acetone in Pairs for HAP-Ca Catalyst on Selectivity of Methylphenol.

[0044] Methanol, ethanol and acetone mixedly fed in pairs are subjected to catalytic reaction testing in a fix bed reactor. Reaction conditions are as follows: the catalyst is filled in a fix bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300 C., the weight hourly space velocity is 1 h.sup.1, the total flow of the reaction gas is 30 mL/min, and the conversion rates of methanol and ethanol and the selectivity of methylphenol under different reactant feeding are shown in Table 7.

TABLE-US-00007 TABLE 7 Effect of Different Reactant Feeding on Selectivity of Methylphenol in Reference Example 2 Methyl- Methanol Ethanol phenol Methanol Ethanol Acetone Conversion Conversion Selec- (kPa) (kPa) (kPa) Rate/% Rate/% tivity/% 4 2 0 9.3 25.0 0 6 0 1 19.9 2.6 0 6 1 28.2 0.4

[0045] As shown in Table 7, when methanol and ethanol are fed in a mixed manner, only aliphatic alcohols are produced, and no methylphenol is detected. When acetone is fed together with methanol and ethanol respectively in a mixed manner, only a small amount of methylphenol is detected in the product, which indicates that acetone exists as a substrate that can form cresol, but methylphenol can be produced in a large amount only when three substrates are cross-coupled.

Reference Example 3

Effect of Other Acid-Base Catalysts on Selectivity of Methylphenol During Common Feeding of Methanol, Ethanol and Acetone.

[0046] Methanol, ethanol and acetone as reactants are subjected to coupling-aromatization reaction in a fix bed reactor. Catalytic reaction testing is carried out in the fix bed reactor. Reaction conditions are as follows: 200 mg of catalyst is filled in a fix bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300 C., the weight hourly space velocity is 1 h.sup.1, the total flow of the reaction gas is 30 mL/min, the partial pressure of methanol is 4 kPa, the partial pressure of ethanol is 2 kPa, the partial pressure of acetone is 1 kPa, and the ratio of the partial pressures of methanol, ethanol and acetone is 4:2:1. The conversion rates of methanol and ethanol and the selectivity of methylphenol under different catalysts are shown in Table 8.

TABLE-US-00008 TABLE 8 Catalytic Performance of Different Acid-Base Catalysts in Reference Example 3 Methanol Ethanol Product Selectivity/% Temperature/ Conversion Conversion Aliphatic C.sub.6-12 C.sub.6 Methyl- Catalyst C. Rate/% Rate/% alcohol ketone ring Alkene Arene Ethers phenol None 300 0 0 ~0 MgAlO 300 16.2 15.3 40.2 10.7 2.4 5.0 ~0 Co-MgAlO 300 25.6 32.6 43.7 23.3 9.6 6.4 ~0 Beta 300 100 100 5.4 44.9 0.5 zeolite Al.sub.2O.sub.3 300 87.5 79.3 100 ~0 SiO.sub.2 300 14.5 22.5 87.6 12.4 ~0 Note: The C.sub.6 ring includes cyclohexanol, cyclohexanone, cyclohexene ketone and other oxygen-containing intermediates containing six-membered rings.

[0047] As shown in Table 8, no reaction occurs in the absence of a catalyst. When other recognized acid-base catalysts are used, high carbon alcohol, alkene and high carbon ketone are more inclined to form in the products due to mismatch of acid-base sites, so the hydroxyphosphate catalyst is preferred in the reaction.