NL2006561C2

NL2006561C2 - Process to prepare an ethanol-derivate.

Info

Publication number: NL2006561C2
Application number: NL2006561A
Authority: NL
Inventors: Meindert Lippits; Bernard Egbert Nieuwenhuijs
Original assignee: Univ Leiden
Priority date: 2011-04-06
Filing date: 2011-04-06
Publication date: 2012-10-09
Also published as: WO2012138221A2; WO2012138221A3

Abstract

The invention is directed a process to prepare a catalyst composition comprising a gamma-alumina carrier, metal nano-particles, wherein the metal is selected from silver, copper or gold, and an additive selected from the group of an alkaline metal compound as present as an oxide or hydroxide of the alkaline metal wherein: in a first catalyst preparation step a gamma-alumina carrier is contacted with an aqueous solution comprising a salt of the alkaline metal in an impregnation step to obtain a loaded alumina carrier,and wherein the weight of alkaline metal as deposited on the alumina surface of the alumina carrier is greater than the weight of alkaline metal as present in the final catalyst composition, drying the loaded alumina carrier and subjecting the dried loaded alumina carrier to a calcination step, loading the silver, copper or gold metal to the calcined loaded carrier in a second catalyst preparation step by contacting with an aqueous solution of a silver, copper or gold metal salt and drying to obtain the catalyst.

Description

PROCESS TO PREPARE AN ETHANOL-DERIVATE

FIELD OF THE INVENTION

The invention is directed to prepare an ethanol-derivate. The invention 5 is especially related to prepare ethylene oxide, diethyl ether or ethylene or any mixtures comprising these ethanol-derivatives.

BACKGROUND OF THE INVENTION

Processes to prepare ethylene from ethanol is described in US-A-4847223. In this process ethanol in admixture with water is reacted to 10 ethylene in the presence of a ZSM-5 containing catalyst onto which triflic acid has been incorporated.

EP-A-1792885 describes a process to convert ethanol into ethylene in the presence of a heterogeneous catalyst consisting of a heteropolyacid.

EP-A-1861196 describes a process for preparing ethylene oxide by 15 epoxidation of ethylene with oxygen using a silver based catalyst. The ethylene oxide may be converted to ethylene glycol, ethylene glycol ether or ethanol amine according to this publication.

M.J. Lippits, B.E. Nieuwenhuys, Catalysis Today 154 (2010) 127-132 describes the direct conversion of ethanol into ethylene oxide on copper and 20 silver nanoparticles.

M.J. Lippits, B.E. Nieuwenhuys, Journal of Catalysis 274 (2010) 142-149 describes the direct conversion of ethanol into ethylene oxide on gold-based catalysts.

Ethanol is an interesting feedstock in that it can be prepared from 25 various sources of biomass. There is a widespread interest to develop processes to prepare various chemical products from ethanol. The present invention is in particular directed to a novel process to prepare ethylene, diethyl ether and/or ethylene oxide directly from ethanol.

SUMMARY OF THE INVENTION

30 This object is achieved by the following process. Process to prepare an ethanol-derivate compound or compounds by reacting ethanol in the presence of a catalyst comprising a gamma-alumina carrier, metal nano-particles wherein the metal is selected from silver, copper or gold, wherein the process is performed in a reactor comprising the catalyst, to which reactor a gaseous 2 feed comprising ethanol, oxygen and an optional diluting gas is supplied and from which reactor an effluent is discharged comprising the ethanol-derivative compound or compounds, oxygen and the optional diluting gas.

Applicants found that with the above process desirable ethanol-5 derivates can be obtained in a high selectivity and yield. Furthermore the process may be performed at relatively low pressures. Additional advantages shall be discussed below when discussing the various preferred embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

10 Figure 1 is the ethylene oxide selectivity for various catalysts as a function of temperature.

Figure 2 is the diethyl ether selectivity for various catalysts as a function of temperature.

Figure 3 is the ethylene selectivity for various catalysts as a function of 15 temperature.

Figure 4 is the ethylene oxide and carbon dioxide selectivity for a catalyst as a function of temperature.

Figure 5 shows the ethanol conversion at different temperatures for different copper based catalysts.

20 DETAILED DESCRIPTION OF THE INVENTION

The ethanol feedstock may be chemically prepared, for example from synthesis gas, i.e. a mixture of carbon monoxide and hydrogen or derived from biomass, i.e so-called bio-ethanol. An example of bio-ethanol is ethanol produced by the fermentation of corn or sugar cane. Other sources for 25 preparing bio-ethanol are non-food biomass sources such a cellulose or algae.

Applicants have found that the process according to the invention can be used to prepare a wide variety of ethanol derivates like ethylene oxide, diethyl ether or ethylene or any mixtures comprising the ethanol-derivatives. Processes which are performed in the presence of oxygen have found to yield 30 ethylene oxide or ethylene as a major product while maintaining a low level of CO and CO2 formation. Examples of by-products that are formed are di- ethylether which is a valuable by-product in its own right. Di-ethylether can be 3 isolated and used as fuel component, for example in an aviation fuel composition or in a diesel formulation.

The molar ratio of ethanol and molecular oxygen is preferably between 1:0.5 and 1:10. A higher oxygen content is not advantageous because the 5 selectivity to the desired ethanol-derivative compounds will be lower and more carbon dioxide will be formed. Lower oxygen content will result in coke formation and catalyst deactivation. The temperature is preferably between 100 and 450 °C. The oxygen may be diluted with a gas, such as argon, helium, nitrogen or carbon dioxide. The oxygen may also be present as part of air or 10 enriched air. The pressure at which the process is performed is preferably between 0.1 and 1 MPa. The gas hourly space velocities (GHSV) are suitably in the range of from 500 to 5000 h-1.

The catalyst comprises a y-alumina carrier (gamma-alumina; Y-AI2O3).

The y-alumina used to prepare the catalyst may comprise small amounts of 15 metals. Applicants found that a suited catalyst can be prepared starting from a Y-alumina carrier comprising between 0.05 and 0.2 wt% of sodium oxide (calculated as Na20) and between 0.01 and 0.1 wt% of an iron oxide (calculated as Fe203).

The metal nano-particles preferably have an average size of below 10 20 nm and more preferably below 5 nm as determined by XRD. When the XRD technique does not detect particles an average particle size of below 3 nm is concluded. The presence of nano-particles can be confirmed using High Resolution TEM. The metal of the nano-particles is selected from silver, copper or gold. The content of copper in the catalyst is preferably between 0.1 25 and 5 wt%. The content of silver in the catalyst is preferably between 0.1 and 5 wt%. The content of gold in the catalyst is preferably between 0.5 and 10 wt%, more preferably between 0.5 and 6 wt%. The surface area of the catalyst is preferably between 250 and 275 m2/g.

The preference for a metal will depend on the desired ethanol-30 derivative to be prepared. Applicants found that ethylene as the ethanol derivative compound can be prepared in a high yield using a catalyst wherein the nano-particles are copper nano-particles. Preferably the temperature for this process is between 350 and 450 °C. This process is advantageous 4 because it uses a relatively simple catalyst, i.e. not containing any molecular sieves, and because of its high yield achievable at moderate operating pressures.

To prepare ethylene oxide as the ethanol-derivative compound it has 5 been found advantageous to use a catalyst also comprising an additive selected from the group of a cerium compound or an alkaline metal compound. The cerium compound is preferably CeOx wherein x is 1,2 or 1.5. Preferably the additive is an alkaline metal compound selected from the group consisting of Na, Li or K and more preferably Li. The alkaline metal compounds may be 10 present in the catalyst as an oxide or hydroxide. Alkaline metal compound in the fresh catalyst, before use in the process of the present invention, will most likely be present as an oxide. The preferred Li metal compound will then be present as Li20. When reference is made to the content of said additives it is assumed that the Ce or alkaline metal is present in its oxide form. The content 15 of these additives in the catalyst is preferably between 1 and 15 wt%. The preferred additive is Li20 because for example processes using a Li2Ü based catalyst according to the present invention have shown a high selectivity in the one step process to ethylene oxide. The gold, copper and silver based catalyst comprising also Li2Ü are all suited to convert ethanol in a high yield 20 at relatively low temperatures to ethylene oxide. The gold based catalyst is preferred because it has shown the highest activity and selectivity in our experiments.

Applicants have shown that a high selectivity and yield in a one step process to ethylene oxide is possible with a catalyst comprising either one of 25 these metals and Li20 as the additive. The fact that ethylene oxide can be prepared in a one step process from ethanol is very advantageous because it eliminates the need to first prepare ethylene as an intermediate as in the prior art processes. Further advantages are that the process is performed at relatively low temperatures and at low pressures. The temperature is 30 preferably between 100 and 250 °C.

The catalyst is preferably reduced before use. More preferably by contacting the catalyst with hydrogen, more preferably 4% hydrogen diluted in Helium or Argon at an elevated temperature of around 400 °C. The catalyst 5 may be regenerated after a period of use by removing carbon deposited on the catalyst by contacting the catalyst with a gaseous stream comprising an oxygenate, preferably oxygen at temperatures between 300 and 400 °C.

The catalyst can have any form when used in the process according to 5 the invention, like for example crushed particles, tablets or extrudates. The catalyst may also be present as a coating on a support or as a reactive layer on the interior of a conduit through which reactants are supplied. The catalyst comprising gold and its preparation is known and described in WO-A-2006/065138. Catalyst based on silver and copper and their preparation are 10 known and described in Catalysis Today 145 15 July 2009, pages 27-33.

Contacting the ethanol with the catalyst may be performed in any type of reactor comprising the catalyst and suited for contacting the gaseous feed with the heterogeneous catalyst. The process is performed in a reactor comprising the catalyst, to which reactor a gaseous feed comprising ethanol, 15 oxygen and preferably a diluting gas is supplied and from which reactor an effluent is discharged comprising the ethanol-derivative compound or compounds, oxygen and the optional diluting gas. Examples of suitable reactors are fluidized bed reactors and packed bed reactors. Fluidized bed reactors are advantageous because catalyst can be more easily regenerated 20 to remove any carbon deposits on the catalyst and the temperature in the reactor can be easily regulated to be within the desired temperature range. Packed bed reactors are advantageous because the catalyst will be less exposed to attrition as will be the case in a fluidized bed reactor. Preferred packed bed reactors are single tubular or multi-tubular reactors. The reaction 25 is exothermic and cooling is suitably applied to maintain a temperature in the range suited for achieving a high selectivity to the desired ethanol-derivative compound. Cooling can be achieved by external cooling the conduit containing the catalyst or by internal cooling by dilution of the ethanol/oxygen feed with a gas, like for example the earlier listed dilution gases argon, helium, 30 nitrogen or carbon dioxide. External cooling can be evaporating water.

Catalysts may also be present as a coating on the interior of the reactor, for example coated on a network which is fixed in the reactor or on the inside of the reactor transport conduits, like in a micro-channel reactor, as for example described in WO-A-2010009021 or in a monolith type reactor..

6

To achieve the highest yield to the desired products it may be advantageous to convert only part of the ethanol when contacting ethanol with the catalyst and recycling any non-converted ethanol to the reactor. In this process ethanol will be separated from the effluent of the reactor, preferably 5 by means of distillation. Preferably the ethanol which is recycled to the feed of the reactor comprises less than 10 vol% water. This to avoid a build-up of water which is disadvantageous for the catalyst stability. Preferably oxygen is also recycled to the reactor. Carbon dioxide is one of the by-products of the present process. In a preferred embodiment of the invention carbon dioxide is 10 recycled to the reactor to act as diluent for the ethanol feed.

The ethylene oxide as prepared in the above process may be advantageously be further converted into ethylene glycol, an ethylene glycol ether or an ethanol amine. The conversion into ethylene glycol or the ethylene glycol ether may comprise, for example, reacting the ethylene oxide with 15 water, suitably using an acidic or a basic catalyst. Suitably the gaseous effluent of the reactor in which the ethylene oxide is formed, as described above, can be directly contacted with such an aqueous solution, for example an aqueous solution containing sodium hydroxide, in a process to prepare ethylene glycol. In another process for making predominantly the ethylene 20 glycol and less ethylene glycol ether, the ethylene oxide may be reacted with a ten fold molar excess of water, in a liquid phase reaction in presence of an acid catalyst, e.g. 0.5-1.0 %w sulfuric acid, based on the total reaction mixture, at 50-70 °C at 100 kPa absolute, or in a gas phase reaction at 130-240 °C and 2000-4000 kPa absolute, preferably in the absence of a catalyst. If the 25 proportion of water is lowered the proportion of ethylene glycol ethers in the reaction mixture is increased. The ethylene glycol ethers thus produced may be a di-ether, tri- ether, tetra-ether or a subsequent ether. Alternative ethylene glycol ethers may be prepared by converting the ethylene oxide with an alcohol, in particular a primary alcohol, such as methanol or ethanol, by 30 replacing at least a portion of the water by the alcohol. The ethylene oxide may be converted into ethylene glycol by first converting the ethylene oxide into ethylene carbonate by reacting it with carbon dioxide, and subsequently hydrolyzing the ethylene carbonate to form ethylene glycol. For applicable methods, reference is made to US-A-6080897, which is incorporated herein 7 by reference. The conversion into the ethanol amine may comprise reacting ethylene oxide with an amine, such as ammonia, an alkyl amine or a dialkyl amine. Anhydrous or aqueous ammonia may be used. Anhydrous ammonia is typically used to favor the production of mono ethanol amine. For methods 5 applicable in the conversion of ethylene oxide into the ethanol amine, reference may be made to, for example US-A-4845296, which is incorporated herein by reference.

Ethylene glycol and ethylene glycol ethers may be used in a large variety of industrial applications, for example in the fields of food, beverages, 10 tobacco, cosmetics, thermoplastic polymers, curable resin systems, detergents, heat transfer systems, etc. Ethanol amines may be used, for example, in the treating ("sweetening") of natural gas.

The invention is thus also directed to a process to prepare ethylene glycol, an ethylene glycol ether or an ethanol amine from ethanol by first 15 preparing ethylene oxide according to the process described above and converting ethylene oxide as obtained into the desired ethylene glycol, an ethylene glycol ether or an ethanol amine.

The invention shall be illustrated by the following non-limiting examples. EXAMPLES

20

Example 1

The gold comprising catalysts also comprising ceria (denoted as CeOx) and/or Li2Ü used in the experiments were prepared by pore volume impregnation of y-Al203(as obtained from BASF, De Meern (NL), sample 25 code: AI-4172 Lot: PP10 ) with the corresponding nitrates.

The Y-AI2O3 was analysed by means of an XRF scan which swowed that it contained ± 0.05 wt% Na20, ± 0.1 wt% SiC>2 and ± 0.05 wt% Fe2Ü3. When preparing the catalyst containing both CeOx and Li2Ü first the CeOx was impregnated followed by impregnation of the U2O. After calcination at 30 350 °C, these oxides were used as support for the Au particles. The prepared mixed oxides had an intended Ce/AI and Li/AI molar ratio of 1/15. The gold catalysts were prepared via homogeneous deposition precipitation using urea 8 as precipitating agent. The appropriate amount of HAuCl4-3aq (99.999%

Aldrich chemicals) was added to a suspension of purified water (18.2 MÜ cm resistive Milli-Q water.) containing the mixed oxide or the Y-AI2O3 in order to prepare a catalyst not containing a CeOx or U2O additive. The intended Au/AI 5 molar ratio was 1/75. This ratio of 1:75 is equal to 5 wt% Au. The temperature was kept at 80 °C allowing urea (p.a., obtained from Acros) to decompose ensuring a slow increase in pH. When a pH of around 8-8.5 was reached, the slurry was filtrated and washed thoroughly with ultra pure (18.2 MQ cm resistive Milli-Q water.)water until no Cl was detected in the solution. The 10 chlorine concentration was tested by titration with AgN03. The catalyst was dried overnight at 80 °C. The catalysts were thoroughly ground to ensure that the macroscopic particle size was around 200 pm.

The gold and Ce and Li concentrations were determined by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) using a Varian 15 Vista-MPX. For that purpose, a small fraction of the catalyst was dissolved in diluted aqua regia.

X-ray diffraction measurements were taken using a Philips Goniometer PW 1050/25 diffractometer equipped with a PW Cu 2103/00 X-ray tube operating at 50 kV an 40 mA. The average particle size was estimated from 20 XRD line broadening after subtraction of the signal from the corresponding support by using the Scherrer equation as described in P. Scherrer, Nachr. K. Ges. Wiss (1918) 98. [32] A.C. Gluhoi, N. Bogdanchikova, B.E. Nieuwenhuys, J. Catal. 229 (2005) 159. The average gold particle size of the catalysts could not be determined by XRD because the size of the particles was below the 25 detection limit of 3 nm. The presence of such small nano-particles were confirmed using High Resolution TEM.

The total surface area was determined by N2 adsorption using a Qsurf M1 analyzer (Thermo Finnigan).

30 The properties of the catalyst thus obtained is listed in Table 1.

Table 1 catalyst Au Au-CeOx Au-Li20 Au-Ü20/Ce0x 9

Metal loading 4.6 ± 0.1 4.1 ± 0.1 4.5 ± 0.3 4.0 ± 0.2 (wt%)

Average gold 4.3 ±0.1 <3.0 3.2 ±0.1 <3.0 particle size (nm)

Total surface 260 ± 5 218 ±7 278 ± 7 262 ±7

area SBET

(m2/g)

Example 2

Example 1 was repeated except that instead of gold a copper comprising catalyst was prepared using Cu(NC>3)2.3aq. The properties of the catalyst thus obtained is listed in Table 2.

5 Table 2

Catalyst Cu Cu-CeOx CU-U2O

Metal loading 1.5± 0.1 1.0± 0.1 1.4 ±0.1 (wt%)

Average copper 3.5 ± 0.1 <3.0 <3.0 particle size (nm)

Total surface area 259±10 253 ±10 268 ±10 SBET (m2/g)

Example 3

Example 1 was repeated except that instead of gold a silver comprising catalyst was prepared using AgNC>3. Because urea and silver atoms can form 10 a soluble Ag[NH3]2+ complex, a large surplus of silver was needed to deposit enough silver on the AI2O3. The properties of the catalyst thus obtained is listed in Table 3.

Table 3

Catalyst Ag-CeOx Ag-Li20

Metal loading (wt%) 1.7 ± 0.1 2.2 ± 0.1

Average silver particle <3.0 <3.0 size (nm) 10

Total surface area 260 ± 10 270 ± 10 SBET (m2/g)

Example 4 (ethanol oxidation in an EtOH/O? mixture of 1)

The activity of the catalysts were measured in a microreactor system. Oxygen flow balanced in argon was bubbled through a vessel containing 5 absolute ethanol. This gas flow was led to a lab-scale flow reactor made from quartz with an internal diameter of 1 cm. In the reactor, the catalyst was placed on a quartz bed. The amount of catalyst used was 0.3 g for the Au-CeOx catalyst. For the AU-U2O, the amount of catalyst was adjusted in such a way that the amount of gold was similar as for the Au-CeOx catalyst. Prior 10 to the activity experiments, the catalysts were reduced with H2 (4 vol% in Ar) at 400 °C for 2 hours.

The oxygen/ethanol as used as feed had a oxygen: ethanol molar ratio of 1:1. Ethanol used consisted of 96 vol.% ethanol and 4 vol.% water. In the experiments a total gas flow of 40 ml-1 (GHSV ~ 2500 h_1) was maintained.

15 The effluent stream was analyzed on-line by a gas chromatograph (HP 8590) with a CTR1 column (Alltech) containing a porous polymer mixture, an activated molecular sieve and a Hayesep Q column (Alltech). All possible reaction products were calibrated by injecting a dilute solution directly into the GC or in case of gases as ethylene and ethylene oxide, the gas flow from 20 lecture bottles was diluted with argon and led to the GC. Mass spectrometry confirmed that the analysis of the reaction products by gas chromatography was correct. To distinguish the different components, the relative intensity ratios of masses 15, 29, 43, 44, 45 were used. The experiments were carried out at atmospheric pressure. Each reaction test consisted of at least two 25 heating-cooling cycles from room temperature up to 400 °C, with a rate of 2 °C /min in order to monitor possible catalyst deactivation and hysteresis processes.

In the first heating cycle the reaction starts at higher temperatures compared to the cooling step. In the subsequent cycles, the behaviour is 30 rather similar to that of the first cooling step. The conversion starts at 100 °C

11 and reaches a maximum at about 275 °C. The AU/U2O/AI2O3 shows the best activity. The oxygen conversion starts at higher temperatures compared to the ethanol conversion. The presence of U2O or CeOx lowers the temperature of oxygen uptake by 50 °C. The oxygen conversion starts at 150 °C and reaches 5 a maximum conversion at 250 °C for the CeOx containing catalysts, and for the AU/U20/AI2O3, the oxygen conversion reaches maximum conversion at 350 °C. At temperatures between 100 °C and 250 °C, the main product is ethylene oxide. This is illustrated in Figure 1 which shows the selectivity to ethylene oxide at various temperatures for the different catalysts. The open 10 circles represent the results for the Au catalyst of Example 1 not containing a CeOx or U2O additive, the open diamonds represent the results for the Au- □20 catalyst of Example 1, the open boxes represent the results for the Au-CeOx catalyst of Example 1 and the triangles represent the Au-Li20/Ce0x catalyst of Example 1. As can be seen in Figure 1 the catalyst with the best 15 performance in ethylene oxide formation is AU-U2O catalyst. A selectivity to ethylene oxide of 88% is achieved. With this catalyst, also traces of the combination product of ethylene oxide and ethanol (ethoxy-ethanol) were detected. When the gas flow was bubbled through a diluted NaOH solution, glycol was produced, which is further evidence that the output gas flow 20 contained ethylene oxide. At temperatures between 250 and 400 °C, diethyl ether was formed over the two CeOx -containing catalysts, as shown in Fig. 2.

Figure 2 shows the selectivity to diethyl ether at various temperatures for the different catalysts. The addition of ceria to the AU/AI2O3 catalyst also results in more ethane formation (not shown). Also, ethylene and CO2 and traces of 25 CO were formed as shown in Figs. 3 for ethylene.

Example 5 (ethanol oxidation in an EtOH/O? mixture of 61

Example 4 is repeated except that the ethanol: oxygen molar ratio was 1:6. The results of ethanol oxidation over the AU-U2O catalyst of Example 1 is 30 in excess oxygen (molar ethanol/02 = 1/6) is presented in Figure 4. It has been observed that ethanol starts to convert at 150 °C and a sharp increase in 12 conversion is observed at 200 °C. At this temperature, also the O2 conversion and the CO2 production start. At temperatures above 300 °C, ethanol is mainly oxidized to CÖ2- The ethylene oxide production can be assigned to the activity of gold as the C-AI2O3 support produces no ethylene oxide. Addition of 5 U2O has shown to increases the ethanol conversion between 50 and 200 °C as compared to the catalysts not containing an additive or containing a CeOx additive. The catalyst comprising U2O and not containing CeOx also showed a better activity at lower temperatures than the Au-Li20/CeOx catalyst. The main product in this temperature region of 50 to 200 °C is ethylene oxide, 10 while no oxygen is consumed.

Example 6

Example 4 was repeated using the Ag-Li20 catalyst of Example 3 and the CU-Ü2O catalyst of Example 2. The results at various temperatures are 15 presented in Table 4.

o

4-J

:> g _ 0 i? > o : D^F: - cd coco o o CO CD O- O CM CM O CM CM O CO 03 T3

O

H—» ^ 0 > £ „___ 'o ® S?

Ü2 p O

<D £ C -r- 00 CM

CO 0 O OCOO CM CO O v- CM

CD

O ~

X

>> o -t; cd * ’"5 © 5? <D :£ F ^ t-OCD o o u> W ® o o) N- t— O) in co O) t-^- o'

C

O

-pr '(/) O s—

C CD

C o o o

±=o OOOCOOOOCMO

LU O COO's-LOGJ's-h'-CS)'^-

CD

co S.

—i 13 -*—»

CD

1_

CD

Q.

E rr- OOOOOOOOO

cd O OOOOOOOOO

h- SL- NCO'tCMCO^-CMCO^ m o o o

_>> CM £J .CM

CD —J _1 —! ro =s cd =5 O < < ü _____I_1__I_I__!_1 M-

_CD

.Q

CD

H

in O m r—-^ r-—t 14

Example 7

Example 4 was repeated with the copper-based catalysts as prepared in Example 2. The selectivities (expressed in mol%) to ethylene, acetaldehyde, diethyl ether, CO and ethylene oxide re presented in Table 5. The ethanol 5 conversion in the first heating stage and in the cooling stage is shown in Figure 5.

The circles represent the results for the Cu catalyst not containing a CeOx or U2O additive, the diamonds represent the results for the CU-U2O

catalyst of Example 2, the boxes represent the results represent the results for 10 the Cu-CeOx catalyst. The closed symbols are the results for the first heating stage. The closed symbols are the results for the cooling stage.

This example illustrates that a process wherein the copper catalyst with and without the additive is used can prepare ethylene in a high yield at a temperature between 350 and 450 °C. A process with a copper-catalyst not 15 containing the additive shows the highest yield to ethylene.

CD

C

f CD

"O

£ '>< o o o o 10 UJ o h- 10 o o cm o 05 t- 'st- Q o o co o o

0 COCMOOLO^v-OCM

i_ 0 sz A-*

CD

Q ooooooot-cm 0 T3 x: 0 33 co -+—> 0

O LO CM

CO Ov-OO LOOO -s— CM

0 c 0 ^ o

£ CO O CD CD CD CD

0 O'v-’t-OCMCOOCOCJ) 0

«O sZ

=5 -4—»

TO

i_ 0 Q.

E o o o o ooo oo 0>Joooo ooo oo i— 2-- CM CO ^ CM CO CM CO ^

oo O O

_>» 0 .CM

LO TO ^ "T1 O) CO D D =3 s O O o o £3 ---------- in o <r>

r—i r—H

Claims

1. Werkwijze voor het bereiden van een ethanol-derivaatverbinding of -verbindingen, door 5 middel van het laten reageren van ethanol in aanwezigheid van een katalysator omvattende een gamma-alumiumdrager, metalen nanodeeltjes waarbij het metaal geselecteerd wordt uit zilver, koper, of goud, waarbij de werkwijze wordt uitgevoerd in een reactor die de katalysator bevat, waarbij aan de reactor een gasvormige aanvoerstroom wordt toegevoegd die ethanol, zuurstof, en eventueel een oplossend gas 10 bevat, en waarbij uit de reactor een effluent wordt afgevoerd dat de ethanol- derivaatverbinding of-verbindingen bevat, alsook zuurstof, en eventueel het oplossende gas.A method for preparing an ethanol-derivative compound or compounds, by reacting ethanol in the presence of a catalyst comprising a gamma-alumium support, metal nanoparticles wherein the metal is selected from silver, copper, or gold, wherein the process is carried out in a reactor containing the catalyst, wherein a gaseous feed stream is added to the reactor containing ethanol, oxygen, and optionally a dissolving gas, and wherein an effluent is discharged from the reactor containing the ethanol-derivative compound or compounds, as well as oxygen, and optionally the dissolving gas.

2. Werkwijze volgens conclusie 1, waarbij de reactor een wervelbedreactor is. 15The method of claim 1, wherein the reactor is a fluid bed reactor. 15

3. Werkwijze volgens conclusie 2, waarbij de reactor een gecompacteerd-bedreactor is.The method of claim 2, wherein the reactor is a compacted bed reactor.

4. Werkwijze volgens een der conclusies 1-3, waarbij uit het effluent niet-omgezet ethanol wordt afgescheiden uit het reactoreffluent, wordt gerecycleerd in de aanvoerstroom, en 20 minder dan 10 vol.% water bevat.4. Process according to any of claims 1-3, wherein unreacted ethanol is separated from the effluent from the reactor effluent, is recycled in the feed stream, and contains less than 10% by volume of water.

5. Werkwijze volgens een der conclusies 1-4, waarbij de y-aluminiumdrager die wordt gebruikt om de katalysator te bereiden, tussen 0,05 en 0,2 gew.% natriumoxide bevat, alsook tussen 0,01 en 0,1 gew.% van een ijzeroxide. 25The process according to any of claims 1-4, wherein the γ-aluminum support used to prepare the catalyst contains between 0.05 and 0.2% by weight of sodium oxide, as well as between 0.01 and 0.1% by weight. % of an iron oxide. 25

6. Werkwijze volgens een der conclusies 1-5, waarbij de metalen nanodeeltjes een gemiddelde afmeting bezitten die kleiner is dan 5 nm, zoals bepaald aan de hand van XRD.The method of any one of claims 1-5, wherein the metal nanoparticles have an average size that is less than 5 nm as determined by XRD.

7. Werkwijze volgens een der conclusies 1-6, waarbij de katalysator een additief omvat dat geselecteerd wordt uit de groep van ceriumverbindingen of aardalkalimetaalverbindingen.The method of any one of claims 1-6, wherein the catalyst comprises an additive selected from the group of cerium compounds or alkaline earth metal compounds.

8. Werkwijze volgens conclusie 7, waarbij het additief een alkalimetaalverbinding is die geselecteerd wordt uit de groep die gevormd wordt op basis van Na, Li, of K.The method of claim 7, wherein the additive is an alkali metal compound selected from the group formed on the basis of Na, Li, or K.

9. Werkwijze volgens conclusie 8, waarbij de alkalimetaalverbinding Li is, en waarbij het Li-metaal aanwezig is in de katalysator in de vorm van een oxide of van een hydroxide.The process of claim 8, wherein the alkali metal compound is Li, and wherein the Li metal is present in the catalyst in the form of an oxide or a hydroxide.

10. Werkwijze volgens een der conclusies 1-9, waarbij de nanodeeltjes gouddeeltjes zijn.The method of any one of claims 1-9, wherein the nanoparticles are gold particles.

11. Werkwijze volgens een der conclusies 1 -6, waarbij het bereide ethanol-derivaat ethyleen is, en waarbij de nanodeeltjes koperdeeltjes zijn.The method of any one of claims 1 to 6, wherein the prepared ethanol derivative is ethylene, and wherein the nanoparticles are copper particles.

12. Werkwijze volgens conclusie 11, waarbij de temperatuur gelegen is tussen 350 en 450°C. 15The method of claim 11, wherein the temperature is between 350 and 450 ° C. 15

13. Werkwijze volgens een der conclusies 1-10, waarbij de ethanol-derivaatverbinding(en) ethyleendioxide, diëthylether, en/of ethyleen is of zijn.The method of any one of claims 1-10, wherein the ethanol-derivative compound (s) is or are ethylene dioxide, diethyl ether, and / or ethylene.

14. Werkwijze volgens een der conclusies 1-13, waarbij de molverhouding van ethanol ten 20 opzichte van moleculaire zuurstof gelegen is tussen 1:0,5 en 1:10.14. A method according to any one of claims 1-13, wherein the molar ratio of ethanol to molecular oxygen is between 1: 0.5 and 1:10.

15. Werkwijze volgens een der conclusies 1-14, waarbij de druk waarbij de werkwijze wordt uitgevoerd gelegen is tussen 0,1 en 1 MPa, en waarbij de ruimtelijke gassnelheid op uurbasis (gas hourly space velocity - GHSV) gelegen is tussen 500 en 5000 h'1. 25A method according to any one of claims 1-14, wherein the pressure at which the method is carried out is between 0.1 and 1 MPa, and wherein the spatial gas velocity on an hourly basis (gas hourly space velocity - GHSV) is between 500 and 5000 h'1. 25

16. Werkwijze volgens een der conclusies 13-15, waarbij de katalysator nanodeeltjes bevat met een gemiddelde afmeting die kleiner is dan 5 nm, waarbij het additief Li20 is, en waarbij de temperatuur gelegen is tussen 100 en 250°C.A method according to any one of claims 13-15, wherein the catalyst contains nanoparticles with an average size of less than 5 nm, the additive being Li 2 O, and wherein the temperature is between 100 and 250 ° C.

17. Werkwijze voor de bereiding van ethyleenglycol, van een ethyleenglycolether, of van een ethanolamine op basis van ethanol, door eerst ethyleenoxide te bereiden aan de hand van de werkwijze volgens een der conclusies 13-16, zoals die hierboven werden beschreven, en door vervolgens het bekomen ethyleenoxide om te zetten tot het gewenste ethyleenglycol, tot een ethyleenglycolether, of tot een ethanolamine.A process for the preparation of ethylene glycol, an ethylene glycol ether, or an ethanolamine based on ethanol, by first preparing ethylene oxide by the process according to any of claims 13-16 as described above, and then by converting the ethylene oxide obtained to the desired ethylene glycol, to an ethylene glycol ether, or to an ethanolamine.