FI110182B - Manufacturing of olefins, involves adding hydrocarbon stream to oxidizing agent, to form alcohol which is passed to distillate stream and dehydrated to obtain olefin - Google Patents

Abstract

Hydrocarbon stream (1) is added to oxidizing agent (4), passed to a reactor (B) and circulated to a stream (7) of reactor (A) in which alcohol product (8) is formed. The product is passed to separator (D) and to a reactor (E). Subsequently, the product is passed to a gas separator (F) in which the stream (12) is circulated as distillate stream (13) to a zone (D) and dehydrated to form olefin. The aliphatic hydrocarbon stream is passed to a separation zone (A) of the oxidation section (I) and removed as side stream (3). Oxidizing agent is added to side stream and the mixture is passed to reaction zone (B). The oxidizing agent is added to the reactor and the product is circulated within the stream to zone (A) and recovered as residual alcohol product. The alcohol is dehydrated to form olefin by passing the stream to a separator zone (D) of dehydration section (II) and passed as side stream (10) of the reaction zone (E). The side reactor and the product are circulated as stream to a separator zone (D) and olefin is recovered as distillate.

Description

110182

Process for the preparation of α-olefins from alcohols

The invention relates to a process for the preparation of α-olefins from alcohols using a zirconia / alumina catalyst.

It is known to produce olefins by dehydrating alcohol. In the reaction, the alcohol forms an olefin and water, and the reaction is carried out at atmospheric pressure in the temperature range of 100 to 350 ° C. Aluminum oxide catalyst has long been used in the production of olefins from alcohols and the use of several other catalyst materials such as zeolites and magnesium sulfate is also known. Dehydration of alcohols by oxide-based catalysts is a widely studied area, and as an example of an industrial process where the basic reaction is alcohol dehydration, mention may be made of styrene from phenylethanol using T1O2 / Al2O3 as catalyst. Ethylene Butter,:. can also be prepared by dehydrating ethanol using sodium modified! »· ·, V. alumina as catalyst.

V: 20; \ j The formation of olefins from alcohols is a complex reaction which takes place: '· *; several reversible parallel and follow-up reactions, including formation of alkenes from alcohol via an ether intermediate, formation of ethers from alcohols, and possible disproportionation of ethers to alkenes and::: 25 alcohols. Reaction alcohols, catalyst properties and reaction conditions will affect the reaction routes. The activity of the catalyst for the formation of olefins and ethers is also dependent on the reaction temperature. Lower heat • · •; · · I states tend to favor more ether formation and higher heat; # modes of olefin formation.

30 2 110182

JP 07-132 225 discloses a process for the preparation of olefins by dehydrating alcohol using ZvO 2 as a catalyst on a support. The catalyst was prepared by attaching a zirconium oxide sol to a support such as alumina, silica or titanium oxide by spraying a sol suspension or immersing the support in a sol, after which the dried catalyst on the support was heated at 350-850 ° C. The catalyst thus obtained, which has good mechanical resistance, is suitable for dehydration of cyclic and tertiary alcohols such as 1-cyclohexylethanol and tert-butyl alcohol.

EP 0 150 832 discloses a process for the preparation of terminal olefins by dehydration of alcohols by means of a zirconia catalyst. Zirconium oxide is prepared by calcining the zirconium compound at 300-1500 ° C.

The problems of the prior art processes for the preparation of α-olefins from alcohols and the catalysts used in the processes include impurities of the product α-olefins using 1 or 2 alcohols as starting materials and poor selectivity of current sodium-modified γ-alumina catalysts. autumn. The disadvantages of a commercial zirconia catalyst are poor mechanical * ·. . * · 20 Stability and Low Activity in Alcohol Dehydration at Lower Temperatures: '| Patients, at higher temperatures, again generate a large amount of by-products.

* i · «· *: In Kytökivi A, Lakomaa EL, Root A, Österholm H, Jacobs JP, Brongerma HH:" Sequential Saturation Reactions of ZrCU and H2O Vapors in the ::: 25 Modification of Silica and γ-Alumina with ZrC> 2, Langmuir 199 7, 13, 2717-2725 V · discloses a process for the preparation of zirconium oxide on a γ-alumina carrier by atomic layer epitaxy (ALE) from ZrCl4 and water.

* ♦

1 1 m I I

From the foregoing, there is an obvious need for an improved process for the preparation of olefins by dehydration of alcohol.

3, 110182

The invention relates to a process for preparing olefins by dehydrating alcohol.

The process for the preparation of olefins by dehydration of an alcohol according to the invention is characterized in what is claimed.

It has been found that α-olefins can be prepared by selective dehydration of straight-chain or branched, primary or secondary alcohols by means of an active and α-selective catalyst comprising zirconia on alumina. The Zir-10 conium / alumina catalyst is preferably prepared from ZrCl 2 and water by a known atomic layer epitaxy technique or by impregnating a zirconium salt, preferably ZrO (NO 3) 2, onto an alumina support. The content of zirconium in the catalyst is 0.1 to 50% by weight, preferably 5 to 20% by weight, and the chloride content in the catalyst is typically less than 0.3% by weight. The carrier is alumina, which is γ-alumina or Θ-15 alumina and preferably θ-alumina. Suitable alcohols for the dehydration reaction of the invention are primary or secondary C 4 to C 4 aliphatic straight or branched alcohols, and preferably C 6 to C 11 alcohols, yielding the corresponding α-olefins. Preferred alcohols are 1-decanol and 2-octanol. When dehydrating with 1-decanol using zirconium oxide / γ-. 20 alumina catalysts, α-olefin can be obtained with greater than 90% selectivity and, preferably, in the gas phase, the activity of the catalyst is of the same order as commercial γ-alumina.

The selectivity of the dehydration of I 1 · <t · 1-decanol to 1-decene is shown in the following <· 25 as a function of conversion with three different metal oxide catalysts of WHSV. '· Being about 6.

1 · ·

I I

• ·> »I * ·

1 hr M

nm 4 110182

Figure 1.

100 - 90 '~~ 5 80> / / Φ 70 / S n / M / /> 60 // / 3 // «50 // 10 I 40 // ® // 0) 30 // TJ // t · 20 ^ __ 10 ____— ---- 0 -1-1-1-1-1-1-1--1-1- 0 10 20 30 40 50 60 70 80 90 100

% Conversion

Gamma-alumina -o-Theta-alumina • i · Zr02 is gamma-alumina! V. The following Scheme 2 shows the selectivity of decanol dehydration for the product.

25 as a function of time using a ZrC> 2 / y-A ^ C ^ catalyst with a particle size of 0.149 <D <0.35 mm, a temperature in the catalyst bed of 297-292 ° C and WHSV

: i ': about 6.

• »» ·> · · • · ·> * ♦ · · »5 110182

Figure 2.

The selectivity of decanol dehydration to products over time with zirconium oxide / alumina catalyst 5,100 I ---------------------------------- - 90 - —----- == —--- ===== ¾- 80 ------------------------ - ----------- 5? 70 ---- -.....— -------------------------------------- ___________________ 10 - 60 -----------—----——. ------------------------- (0 £ 3? 50 —————————— ..— -> Φ OT 30 ------------------------------------------ ------- 20 ----------------------------------------- 15 1, ° Γ I t ~ ......

100 150 200 250 300 350

Time I min 1-decene '! "20 □ trans-2-decene. *. * * Cis-2-decene::': · other decenes. * · * Didecyl ether '·' - n-decane.

Scheme 3 shows the conversion of decanol dehydration to products over time. ·: '. using various catalysts with a WHSV of about 6 and a temperature of about 300 ° C.

»110182

Figure 3.

Comparison of Catalysts for 1-Decanol Dehydration i 5 120 ----------------------------------------- - 100 ----------------- * * "ά 80-- □ --α —-— --—--

is A

10 ca <0 <0 "60 ------------------------------------------ --------------

c A

a> 0) | 40 —--------------------------------------- --------- ---------------------------- ---------------------- ---------------— T— 20 ............................... ......

15 0 1 --- 1-1 -'- 100 150 200 250 300 350

Time, min "· 20 --------------- --------- ----------- • V; ZrO2 / gamma alumina! □ Gamma alumina * a Theta alumina • 25

When dehydrating 2-octanol using the process of the invention, the maximal selectivity of 1- · octene for the zirconia / γ-alumina catalyst is 49%, whereas for 1-octene alone, the maximal selectivity I · 30 is 45% and respectively for the commercial zirconia To 39%.

7, 110182

Zirconium oxide containing catalysts based on the invention are significantly more active in alcohol dehydration than zirconium containing catalysts disclosed in prior art publications. The activity of the catalyst 5 can be described by the so-called. Turn over frequency (TON). The TON value indicates the number of units of the reacting compound that is reacted per amount of catalyst per unit time. The catalysts of the invention obtain a TON of the same order at about 150 ° C at lower reaction temperatures than previously published zirconium containing catalysts. Case 10 is illustrated in Table 1 below. The TON values for the catalysts of the invention at a reaction temperature of 300 ° C are more than 10 times the previously disclosed catalyst activities.

i · · * 1 <· ·

• I

♦ g 110182 TABLE 1: Comparison of catalyst activity

Reference Temperature, ° C TON g alcohol / g Alcohol ___ catalyst * !! __ EP 0 150 832 360 0.1 * 2-hexanol

Example 2____ EP 0 150 832 370 0.1 * 2-octanol

Ex. 3____ JP 132 225 350 0.7 1-Cyclohexylethanol

Example 1-1 (Table 2) __________ JP 132 225 350 0.6 2-Methyl-2-butanol

Example 1-1 (Table 3) __

Example of Application 230 0.1 230 0.2 3 250 0.8 1-Decanol 250 1.6 300 5.1 300 9.6 __300__9g2__

Ex. 245 3.0 4 241 4.9 2-Octanol 246 2.0 __205__03__

Example 208 0.3 2-Octanol _5__207__03__ ..U 'Example 210 0.5 2-Octanol 6__244__33__ 1 Example 210 0.5 8 209 0.7 2-Octanol 243 4.6 __243__2 / 7__

Example 211 0.7 2-Octanol · 9: 241 5.1

Example 213 0.1 li ' 10 255 2.4 '·': * calculated with a density of ZrCl 2 of 5.68 g / cm 3.

..... 5 110182 9

The process of the invention will now be illustrated by the following comparative examples and some preferred embodiments of the invention, which, however, are not intended to limit the scope of the invention.

EXAMPLE 1: Alternative Example: Dehydration of 1-decanol using commercial γ-alumina.

10 1-decanol was dehydrated using commercial γ-alumina. The alumina BET surface area measured before the dehydration test was 210 m2 / g. The catalyst was tested by dehydrating 1-decanol in a flow reactor at 230 ° C to 300 ° C with WHSV 1.2-11.8. The results are shown in Table 2 below. The sim-selectivity of Mak-15 for 1-decene was 80%.

TABLE 2: Results of Dehydration Experiments on Dehydrogenation of Commercial Decarbonate with Commercial γ-Alumina.

20 __.___ '·'. 'Conditions Results t * * f »-1 --- -, --.- I *', Temperature, WHSV, g Conversion, Selectivity,% ''. 1 ° C 1-decanol /% • · · g catalyst _______ V * 1-decene trans-2-cis-2 other didecyl- _____decene decene decenes ether-230 1.2 54.2 17.2 0.1 0.2 0 82.5 230 6.0 10.5 7.4 0 0 0 92.6 V: 230 11.3 4.4 20.3 0 0 0 79.7 250 1.2 87.1 59 0.9 2 , 9 0.2 37 250 5.6 52.9 13.5 0 0.1 0 86.5. 250 11.6 27.6 18.6 0.1 0.4 0 81 300 1.2 99.8 7.5 28.9 12.6 50.6 0.2 300 5.7 97.6 80 5, 6 12.9 0.5 1.0 300 11.8 90.8 75.7 5.5 10.9 1.1 6.6 ii «.. I-1- 'I-1-1 -—- - «I» * · ·

»I

10 110182 EXAMPLE 2:

Comparative Example: Dehydration of 1-decanol using commercial θ-alumina.

5-Decanol was dehydrated using θ-alumina. The catalyst was prepared by treating commercial γ-alumina at 950 ° C in air for six hours. The alumina BET surface area measured before the dehydration test was 131 m2 / g. The catalyst was tested by dehydrating 1-decanol in a flow reactor at 230 ° C to -10 300 ° C with WHSV 1.1 to 6.2. The results are shown in Table 3 below. The maximum selectivity for 1-decene was 89%.

TABLE 3: Results of Dehydration Experiments on 1-Decanol with θ-Alumina 15

Conditions Results Temperature, WHSV, g Conversion, Selectivity,% ° C 1-decanol /% _______ g catalyst 1-decene trans-2-cis-2 other didecyl. decene decene decenes ether • · · · - —- - - »· · · 230 1,2 32.3 8.9 0 0 0 91.1 230 2.4 14.3 8.5 0 0 0 91.5; 230 3.8 8.1 41.4 0 0 0 58.6 I ”. 230 6.1 3.3 15.0 2.9 2.4 0 79.7:, 1 ·· 250 1.2 78.2 20.0 0 0 0 80.0 250 2.5 62.8 14, 9 0 0.1 0 85.0 '250 3.9 37.5 22.7 0 0.2 0 77.1 250 6.1 55.8 15.0 2.9 2.4 0 79.7' 300 1.1 99.8 31.3 27.9 31.6 9.3 0 300 2.4 100 71.3 9.6 18.2 1.0 0 300 3.8 93.9 89.5 2 5, 3 0 3.1: 300 6.2 82.3 65.1 0.3 1.1 0.2 53.6 · • · · i · • 1 * · ·

EXAMPLE 3: Dehydration of 3: 1-Decanol Using a Zirconia / Y Aluminum Catalyst wherein Zirconia has been prepared from zirconium tetra-5 chloride and water by atomic layer epitaxy.

The 1-decanol was dehydrated using a zirconia / γ-alumina catalyst in which zirconium oxide was prepared from zirconium tetrachloride and water by atomic layer epitaxy (ALE). The BET surface area of the catalyst measured prior to the dehydration test was 163 m 2 / g. The catalyst was tested by dehydrating 1-decanol in a flow reactor at 230 ° C to 300 ° C with WHSV 5.8-12.4. The results are shown in Table 4 below. The maximal selectivity for 1-decene was 93%. As can be seen from the results, zirconium oxide prepared by atomic layer-epitaxial technique increases the 1-olefin selectivity of alumina-15-based catalyst in the dehydration of alcohols.

TABLE 4: Results of dehydration experiments with 1-decanol using zirconia / γ-. an alumina catalyst in which zirconium oxide was prepared on the alumina surface by atomic layer epitaxy.

•,;. · Conditions Results • '· Conversion, Selectivity,% Temperature ° C WHSV, g% 1-decene trans-2-cis-2 other didecyl ·. · · 1-decanol / g decene decene decanes ether __catalyst ___________ 230 5.9 1.8 89.3 0 0 0 10.7 230 12.2 1.5 45.5 0 0 0 54.5 250 5.8 14.2 92.8 0 0.2 0 7.0 250 12.4 12.5 52.0 0 0 0 48.0 • 300 5.9 86.8 91.0 0.7 0.5 0 5.9 ·: ·: 300 12.3 77.8 90.4 0.4 1.8 0.3 7 300 12.4 73.9 86.1 0.4 1.7 0.3 11.3 »12 EXAMPLE 4:? 10182 2-Octanol Dehydration Using Zirconia /? - Alumina Catalyst.

2-Octanol was dehydrated using a zirconia / γ-alumina catalyst in which zirconium oxide was prepared from zirconium tetrachloride and water by atomic layer epitaxy. The catalyst had a zirconium content of 10.5% by weight. The chloride content of the catalyst was less than 0.1 wt%. The catalyst had a BET surface area measured before the dehydration test of 163 m 2 / g. The catalyst was tested by dehydrating 2-10 octanol in a flow reactor at 205 ° C to 246 ° C with WHSV 3.0-12.1. The results are shown in Table 5. The maximum selectivity for 1-octene was 45%.

| EXAMPLE 5: Dehydration of 2-Octanol Using Zirconia / Y Alumina Catalyst.

The 2-octanol was dehydrated using a zirconia / γ-alumina catalyst, 'V'. Wherein the zirconia was prepared on the alumina surface from zirconium tetrachloride and water by atomic layer epitaxy. Zirconium containing catalyst. >,: mouth was 9.5 wt%. The chloride content of the catalyst was 0.1 to 0.2% by weight. The catalyst was tested by dehydrating 2-octanol in a flow reactor at 207 ° C to 208 ° C. WHSV 2-6. The results are shown in Table 5. The maximum selectivity for 1-25 octene was 49%.

EXAMPLE 6: 13 110182 Dehydration of 2-Octanol Using Zirconia / Y Alumina Catalyst.

2-Octanol was dehydrated using a zirconium oxide / Y-alumina catalyst in which zirconium oxide was prepared from zirconium tetrachloride and water by atomic layer epitaxy. The zirconium content of the catalyst was 13.7% by weight. The chloride content of the catalyst was less than 0.2 wt%. The catalyst was tested by dehydrating 2-octanol in a flow reactor at 210 ° C to 244 ° C with 10 WHSV of 2-6. The results are shown in Table 5. The maximum selectivity for 1-octene was 45%.

EXAMPLE 7: Comparative Example 15 Dehydration of 2-octanol using γ-alumina.

2-Octanol was dehydrated using γ-alumina for comparison. Catalyst. was tested by dehydration of 2-octanol in a flow reactor at 206 ° C to 254 ° C at WHSV 2-6. The results are shown in Table 5. The maximum selectivity for 1-octene was 46%.

Λ! EXAMPLE 8: 25 Dehydration of 2-octanol using γ-alumina impregnated

Zr0 (N03) 2.

: 2-octanol was dehydrated using γ-alumina impregnated; ZrO (N03) 2. The catalyst was then calcined at 500 ° C. The zirconium content of the catalyst was 12 wt%. The catalyst was tested in 2-octanol dehydrate 14110182 in a flow reactor at 209 ° C to 243 ° C with WHSV 3-6. The results are shown in Table 5. The maximum selectivity for 1-octene was 48%.

EXAMPLE 9: 5 Dehydration of 2-octanol using γ-alumina impregnated

Zr0 (N03) 2.

2-Octanol was dehydrated using γ-alumina impregnated with 10 ZrO (NO 3) 2. The catalyst was then calcined at 600 ° C. The zirconium content of the catalyst was 12 wt%. The catalyst was tested by dehydration of 2-octanol in a flow reactor at 211 ° C to 255 ° C with WHSV 3-6. The results are shown in Table 5. The maximum selectivity for 1-octene was 49%.

15 EXAMPLE 10: Dehydration of 2-octanol using θ-alumina impregnated

ZrO (NOI) 2.

2-Octanol was dehydrated using θ-alumina impregnated with «· ZrO (NC NC 3) 2 ′. The catalyst was then calcined at 950 ° C. The catalyst had a zirconium content of 12% by weight. The catalyst was tested on 2-octanol dehydra. : operating in a flow reactor at 213 ° C to 255 ° C with WHSV 3-6. Conversions ·; ·. set is shown in Table 5. The maximum selectivity for 1-octene was 49%.

25 is 110182 TABLE 5: Comparison of Catalysts for 2-Octanol Dehydration

Eg Catalyst WHSV T Conversion, _ Selectivity,% _ (° C)% 1-octene 2-octene Other Ethers ________oketenes__ 4 with ZrO γ-alumina 5.9 245 50.6 43.1 50.2 0 6.7

Zr02 SALE *

Zr content 10.5 wt% 12.1 241 40.3 43.2 49.3 0 7.5 3.0 246 65.1 41.3 54.1 0 4.6 ___ 3.0 205 9.6__44.8 36 , 6__0__18.7 5 ZrO 2 with γ-alumina, 2.4 208 14.2 45.8 39.1 0 15.2

Zr02 SALE *

Zr content 9.5 wt% 6.1 207 8.8 48.8 37.7 0 13.4 6 ZrO 2 with γ-alumina, 3.3 210 15.8 45.3 40.1 0 14.6

Zr02 SALE *

Zr content 13.7 wt% 5.8 244 64.6 43.0 50.8 0.04 6.2 7 γ-alumina 1.7 254 99.9 40.2 59.4 0.3 0 2, 8,249 99.8 41.8 58.0 0.2 0 5.7 242 91.6 42.9 56.0 0 1.1 5.7 207 16.9 45.5 35.2 0 19.3 1.8 208 37.0 41.2 37.9 0.03 20.9 2.7 207 27.9 42.8 36.7 0 20.5 ___ 5.6 206 18.8 46.1 36.3__0__17.6 8 ZrO2 with γ-alumina,

Impregnation + 500 ° C calcination 2.7 210 18.1 45.1 35.4 0 19.5 6.0 209 12.2 47.8 34.8 0 17.4 6.0 243 76.8 43.7 51.9 0 , 1 4,2 ___ 2.8 243 95.3__43.2 56.2 0.1__0.5 9 ZrO 2 with γ-alumina,

Impregnation + 600 ° C calcination 3.0 211 23.1 46.3 36.2 0.06 17.5 ___ 6.2 241 81.8 44.1 53.0 0.07 2.8 • | · 10 Zr02 θ alumina, 3.0 213 4.6 49.2 38.7 0.2 11.8 '*' Impregnation + Ύ: 950 ° C calcination 5.8 255 42.0 44.9 46.5 0.5 8 , 1. ·. : 5 * = Atomic Layer Epitaxy

Claims (10)

Process for the production of α-olefins from alcohols, characterized in that a primary or secondary alcohol is dehydrated by means of a zirconium oxide / carrier catalyst, the carrier is alumina and the zirconia / carrier catalyst is prepared by atomic layer epitaxy technology or by impregnation of a zinc -nium salt on a carrier. Process according to claim 1, characterized in that the support is γ-alumina or θ-alumina. 3. A process according to claim 1 or 2, characterized in that the support is Θ-alumina. 15 Process according to any one of claims 1 to 3, characterized in that the zirconia salt is Zr0 (NO3) 2. . . Process according to any one of claims 1-4, characterized in that the catalyst - - '. The zirconium contains 0.1-50% by weight, preferably 5-20% by weight. 20. ·. A method according to any one of claims 1-5, characterized in that the dehydro- ·: ·. the rationing of the alcohol is carried out in gas phase. * · · 7. Use of a Zirconia / Carrier Catalyst Prepared by Atomic Layer Pitaxite Technology in the Dehydration of Primary or Secondary Alcohols. • ·, ·, ·. Use according to claim 7, characterized in that the carrier is aluminum. oxide, advantageous γ-alumina or Θ-alumina and most advantageous. * θ-alumina. . 30 i * »» »» 110182 Use according to claim 7 or 8, characterized in that the catalyst contains zirconium 0.1 - 50% by weight, advantageously 5-20% by weight. Use according to any one of claims 7 to 9, characterized in that the dehydration of the alcohol is carried out in a gas phase. * 1