JP5334114B2 - Propylene production method - Google Patents

Description

  The present invention relates to a method for synthesizing propylene by converting ethanol.

Typical production methods for propylene, a key material of the chemical industry using petroleum as a raw material, are 1) steam decomposition of naphtha at around 900 ° C, 2) dehydrogenation or oxidative dehydrogenation of propane, etc. It is.
On the other hand, it is expected that development of a method for producing propylene from non-petroleum-based raw materials, particularly biomass-derived alcohol, will become more and more necessary in the future due to concerns about the exhaustion of petroleum resources. As a raw material for propylene, ethanol by fermentation is also promising in terms of quantity, and butanol is known to be acetone-butanol fermentation.

  However, although an example of propylene synthesis by dehydration of monovalent isopropanol is known (Patent Document 1), in the production from ethanol, it is necessary to control reactions such as dehydration / dimerization / disproportionation, which is difficult. The degree is high. For example, propylene production from single ethanol using H-ZSM-5 as a catalyst has been reported. Propylene is not the main product, but C5 + hydrocarbons containing aromatics (Non-Patent Document 1), propane ( Non-patent document 2) or ethylene (non-patent document 3) was mainly produced. Further, as the reaction time elapses, the propylene selectivity further decreases and the ethylene selectivity tends to increase, and there is a problem in terms of catalyst durability. Propylene production from a mixed system of ethanol and butanol has also been attempted (Non-patent Document 4). However, since the reaction temperature is as low as about 400 ° C. and it is not zeolite modified with tungsten or the like, C4 or aromatic carbonization is not possible. Hydrogen by-product was intense and the propylene selectivity was not satisfactory.

US Pat. No. 6,441,262

J. Chem. Tech. Biotech., 77, 211-216 (2002) Catal. Lett., 31, 395-403 (1995). Green Chem., 9, 638-646 (2007). The 102nd Catalysis Conference-Discussion Session A Proceedings, September 24, 2008, p. 41

  An object of the present invention is to provide an industrially advantageous new propylene synthesis catalyst capable of synthesizing propylene with increased selectivity and catalyst stability by an ethanol conversion reaction.

  As a result of intensive studies on various catalyst groups in order to solve the above-mentioned problems, the present inventors used zeolite modified with tungsten or the like as a catalyst and carried out a co-reaction of ethanol and an alcohol having 4 or more carbon atoms at about 600 ° C. By reacting under relatively high temperature conditions, the by-product of hydrocarbons having 4 carbon atoms and aromatic hydrocarbons is reduced and propylene selectivity is improved, and the effects of butanol, which is more hydrophobic than ethanol, By controlling the dehydration reaction on the catalyst surface and suppressing dealumination, which is one of the main causes of the decrease in activity, it was found that the durability of the catalyst was also improved and the present invention was completed. It was.

That is, according to this application, the following invention is provided.
[1] A method for producing propylene, comprising reacting ethanol and an alcohol having 4 or more carbon atoms in the presence of H-ZSM-5 zeolite alone or tungsten-modified H-ZSM-5 zeolite .
[ 2 ] The method for producing propylene according to the above [1] , wherein the alcohol having 4 or more carbon atoms is butanols.
[ 3 ] The method for producing propylene according to [1] or [ 2 ] above, wherein one or both of ethanol and butanol is bioethanol or biobutanol obtained by fermentation.

  According to the method of the present invention, propylene can be synthesized from an ethanol raw material such as bioethanol in one step with increased selectivity and durability.

  In the propylene synthesis method used for synthesizing propylene by converting ethanol of the present invention, ethanol and an alcohol having 4 or more carbon atoms such as butanols in the presence of a porous solid oxide are heated at a temperature higher than usual. It is made to react by. Furthermore, it contains a porous solid oxide modified with a compound containing a metal belonging to Group 6 and / or Group 7 of the Periodic Table.

  The porous solid oxide includes any oxide as long as it can coexist with a compound containing a Group 6 and / or Group 7 metal in the periodic table or can carry a compound containing these metals on the surface thereof. .

Typical examples of such porous solid oxides include zeolite compounds, and examples thereof include Y-type, L-type, mordenite, ferrierite, beta-type, and H-ZSM-5.
In addition, examples of porous solid oxides other than zeolite compounds include TS-1, MCM-41, MCM-22, MCM-48, crystalline gallosilicates such as gallosilicate, and large-diameter silica compounds. .

In addition, these porous solid oxides include those containing elements such as titanium, aluminum, vanadium, niobium, tantalum, boron, zirconium, and amorphous porous silica compounds.
Examples of other porous solid oxides include oxides such as mesoporous silica, alumina, zirconia, titania, and ceria.
The porous solid oxide particularly preferably used in the present invention is an H-ZSM having various silica / alumina ratios capable of adsorbing ethanol on the surface and supplying protons to the OH groups of ethanol to promote dehydration. -5 zeolite.

The porous solid oxide used in the present invention is more preferably modified with a compound containing a metal belonging to Group 6 and / or Group 7 of the periodic table.
As a modification method, a method of containing a compound such as tungsten in a solid oxide and firing in air is adopted.

  Here, the compound containing a metal belonging to Group 6 and / or Group 7 of the periodic table means a compound containing at least one metal of chromium, molybdenum, tungsten, manganese, and rhenium.

  Typical examples of the compound containing a metal belonging to Group 6 and / or Group 7 of the periodic table include a tungsten compound, a rhenium compound, a molybdenum compound, and the like, and the tungsten compound includes a halogenated compound such as tungsten chloride. Tungsten, tungstic acid (10-) ammonium decahydrate, ammonium metatungstate, tungstic acid cation compound such as 12 tungstic acid (10-) potassium decahydrate, dodecatungstophosphoric acid (3-) 14 hydrate And tungsten metal hetero compounds such as dodecatungstosilicate (4-) 26 hydrate, organometallic tungsten compounds such as hexacarbonyltungsten and hexamethyltungsten (VI), and the like.

  Examples of the rhenium compounds include inorganic acid salts such as nitrates and sulfates, halides such as chlorides and bromides, rhenic acid compounds such as potassium hexachlororhenate, rhenates such as ammonium perrhenate, decacarbonyl dirhenium (0 ), Organometallic rhenium compounds such as pentacarbonylmethylrhenium, and the like.

  The molybdenum compounds include halides such as molybdenum chloride, molybdenum complex compounds such as 2 molybdenum acetate, organometallic molybdenums such as hexacarbonylmolybdenum (0), sodium molybdate, 7- (6-) ammonium molybdate 4 Examples include molybdate cationic compounds such as hydrates, dodecaboribdophosphoric acid (3-) 30 hydrate, dodeca and dodecamolybdo compounds such as (3-) ammonium ribdophosphate.

As a method of incorporating a compound such as tungsten into the porous solid oxide, a conventionally known method such as a physical mixing method, an impregnation method, a precipitation method, a kneading method, or an incipient wetness method can be employed.
For example, a compound such as tungsten is usually supported on a solid oxide as an aqueous solution. Moreover, organic solvents, such as acetone, isopropanol, and benzene, are also used.
The firing temperature of the zeolite oxide or the like containing a compound such as tungsten is about 300 to 900 ° C, preferably about 500 to 700 ° C.
The supported amount of tungsten or the like is arbitrary, but it is 0.001 to 50 g, preferably 1 to 20 g per 100 g of the carrier oxide as tungsten metal. These additives can be used alone or as a mixture of two or more. In particular, the group 6 tungsten element of the periodic table is particularly preferable because it promotes dimerization of an ethylene intermediate produced by dehydration of ethanol.

  As ethanol used in the present invention, not only reagent-grade ethanol but also ethanol containing water, bioethanol by fermentation, and the like are used. The water content in this case is arbitrary, but 0 to 50 wt%, preferably 0 to 15 wt% is used.

Examples of alcohols having 4 or more carbon atoms used with ethanol in the present invention include alkanols such as butanols, pentanols and hexanols, alkanediols such as butanediols, pentanediols and hexanediols, and pentaerythritol. Examples include polyols.
The amount of introduction of these alcohols having 4 or more carbon atoms is 0.01 to 100 mol, preferably 0.5 to 5 mol, relative to 1 mol of ethanol. In addition, since these alcohols having 4 or more carbon atoms generate olefins such as butenes and pentenes by dehydration under the reaction conditions, these olefins having 4 or more carbon atoms and water are introduced from the beginning. You can also. The amount of these olefins introduced is about the same as that of alcohols having 4 or more carbon atoms, and water is also preferably about the same mole as the alcohol.

In the method of the present invention, ethanol and butanol may be simultaneously converted in the reactor in the presence of the catalyst. In this synthesis reaction, as shown in the following reaction formula, propylene is obtained as a main product. In addition, ethylene, butenes, saturated hydrocarbons having about 1 to 10 carbon atoms, and benzene / toluene / Aromatics such as xylene and water are produced.
C ₂ H ₅ OH + C ₄ H ₉ OH →
C ₃ H ₆ + C ₂ H ₄ + C ₄ H ₈ + C _n H _{2n + 2} (n = 1 to 10) + C ₆ H ₆ + C ₇ H ₈ + C ₈ H ₁₀ + H ₂ O (1) (Considering the coefficient) None)

  The propylene production mechanism is not clear at this time, but it is a complex reaction such as ethanol or butanol dehydration (ethylene or butene production) / disproportionation (propylene production by disproportionation of ethylene and butylene). I believe that. The coexistence of butanol, which is relatively hydrophobic compared to ethanol, promotes the removal of water produced on the catalyst surface by ethanol dehydration, and eliminates the dealumination of zeolite (a major cause of deactivation) that normally occurs under water production conditions. Since it is suppressed to some extent, it is assumed that durability is increased.

The synthesis reaction of propylene of the present invention can be carried out in either a gas phase or a liquid phase, but ethanol has a lower boiling point than water, and propylene is a gas at room temperature, so that separation from the catalyst is considered. Usually, it is carried out in a gas phase system.
The reaction temperature in this case is 50 to 800 ° C., preferably 400 to 650 ° C., and the reaction pressure is arbitrary, and is 0.01 to 100 MPa, preferably 0.05 to 5 MPa.
Usually, ethanol and butanol are introduced into the catalyst layer together with a diluent gas, and an inert gas such as nitrogen or argon, CO ₂ or water vapor is used as the diluent gas.
The use ratio of the dilution gas is 0.05 to 50 moles, preferably 0.5 to 10 moles per mole of ethanol.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
Example 1
[Preparation of 10 wt% W / H-ZSM-5 catalyst]
2 g of H-ZSM-5 (Si / Al ₂ ratio = 280) manufactured by Zeolis Co. were impregnated with 0.27 g of ammonium metatungstate (10 wt% in terms of tungsten), dried at 60 ° C. overnight, and further at 100 ° C. After drying for 3 hours, air calcination was performed at 600 ° C. for 5 hours to obtain 2.18 g of a W / H-ZSM-5 catalyst.
[Propylene synthesis reaction]
10% W / H-ZSM-5 (0.5 g) thus obtained was introduced into a fixed bed flow reactor, and a mixed gas of ethanol, n-butanol and nitrogen (volume ratio (ethanol / n-butanol / nitrogen)). = 30/22/48) at a total pressure of 0.1 MPa, W / F (N ₂ ) = 6.15 mOl (g cat h) ⁻¹ , WHSV (EtOH) = 0.49 h ⁻¹ , WHSV (n− (BuOH) = 0.67 h ⁻¹ , reacted at 600 ° C.
30 minutes after the start of the reaction, the product was analyzed by gas chromatography. As a result, propylene was produced at an ethanol conversion rate of 100%, a propylene selectivity of 40.6%, and a propylene / ethylene ratio of 1.50 (Table 1). As by-products, ethylene 27.0%, butenes 17.0%, BTX (sum of benzene + toluene + xylene) 2.79% (Table 1), C1 to C10 saturated hydrocarbons and small amounts of CO ₂ was detected.

ここでCnは炭素数nの炭化水素、B、T、Xはそれぞれベンゼン、トルエン、キシレンを示す。また*は積を表す。他の炭化水素選択率も同様に計算した。 The ethanol conversion and propylene selectivity were calculated as follows for convenience.

Here, Cn represents a hydrocarbon having n carbon atoms, and B, T, and X represent benzene, toluene, and xylene, respectively. * Represents a product. Other hydrocarbon selectivity was calculated similarly.

(Comparative Example 1)
A synthesis reaction of propylene was carried out in the same manner as in Example 1 except that n-butanol was not used. The results are shown in Table 1.
Ethanol conversion was 76.4% and propylene selectivity was 32.3%, but the propylene / ethylene ratio was 0.82, rather ethylene was the main product.

(Comparative Example 2)
A synthesis reaction of propylene was carried out in the same manner as in Example 1 except that ethanol was not used. The results are shown in Table 1.
The n-butanol conversion was 85.4% and the propylene selectivity was 35.8%, but the propylene / ethylene ratio was 1.14, lower than that of Example 1, and the propylene / propane ratio was 5.63. It was about ½ of Example 1, and there were many by-products of the propane by which the propylene was hydrogenated.

(Examples 2-3)
The synthesis reaction of propylene was carried out in the same manner as in Example 1 except that WHSV (n-BuOH) = 0.33 and 1.04h ⁻¹ . The results are shown in Table 1.
Ethanol conversion, propylene selectivity, propylene / ethylene ratio were 87.2% in Example 2, propylene selectivity 36.2%, propylene / ethylene ratio 1.03, and 88 in Example 3, respectively. The propylene selectivity slightly decreased when the amount of butanol introduced was small.

(Examples 4 to 6)
The Si / Al ₂ ratio of the carrier H-ZSM-5 is 80, 50 and 23, and WHSV (EtOH) and WHSV (n-BuOH) are 1.10, 1.33, 1.35, 1. The reaction was carried out in the same manner as in Example 1 except that 63, 1.98, and 2.3 h ⁻¹ . The propylene selectivity was 35.1%, 36.1%, and 37.5%, respectively. The propylene / ethylene ratios were 1.21, 1.19, and 1.47, which were the same as those in Example 1, respectively.

(Examples 7 to 8)
Using H-ZSM-5 (280) without tungsten modification as a catalyst, the reaction was carried out at 600 ° C. in the same manner as in Example 1, and the products 1 hour and 8 hours after the start of the reaction were analyzed.
After 1 hour, the ethanol conversion was 91%, the propylene selectivity was 37.5%, and the propylene / ethylene ratio was 1.42. However, after 8 hours, the ratio was 60% and 37.8%, and the propylene / ethylene ratio was It showed a tendency to decrease slightly to 1.20.

(Examples 9 to 10)
Using tungsten-modified H-ZSM-5 (280) catalyst, the reaction was conducted in the same manner as in Example 1, and analysis was performed after 1 hour and 8 hours.
After 1 hour, the ethanol conversion was 67.2%, the propylene selectivity was 36.9%, and the propylene / ethylene ratio was 1.25. After 8 hours, 71.3% and 38.6% remained unchanged. The propylene / ethylene ratio showed a tendency to improve slightly to 1.38, and durability was recognized.

(Comparative Example 3)
The reaction was conducted in the same manner as in Example 9 except that ethanol was not used, and analysis was conducted after 1 hour. As a result, the butanol conversion was 45.6%, the propylene selectivity was 30.4%, and the propylene / ethylene ratio was as low as 0.92.

Claims (3)

A process for producing propylene, comprising reacting ethanol and an alcohol having 4 or more carbon atoms in the presence of H-ZSM-5 zeolite alone or tungsten-modified H-ZSM-5 zeolite . The method for producing propylene according to claim 1, wherein the alcohol having 4 or more carbon atoms is butanols. The method for producing propylene according to claim 1 or 2 , wherein one or both of ethanol and butanol is bioethanol or biobutanol obtained by fermentation.