Process for preparing an unsaturated alcohol

Abstract

The present invention relates to a process for preparing an unsaturated alcohol, preferably 3,7-dimethyl-2,6-octadienal, by contacting an alkene, preferably isobutene, with formaldehyde in the presence a condensation catalyst comprising a zeolitic material comprising the framework structure of which comprises a tetravalent element Y other than Si.

Claims

1. A process for preparing a compound of formula (II) ##STR00038## comprising (i) providing a mixture comprising formaldehyde and a compound of formula (I) ##STR00039## (ii) contacting the mixture, provided in (i) with a condensation catalyst comprising a zeolitic material, obtaining a mixture (ii) comprising the compound of formula (II); wherein R.sub.1, R.sub.2 and R.sub.3 are independently of each other selected from the group consisting of H, optionally substituted C.sub.1-C.sub.10 alkyl, optionally substituted C.sub.2-C.sub.10 alkenyl and optionally substituted aryl having from 6 to 12 carbon atoms; wherein the framework structure of the zeolitic material in (ii) comprises Si, O, optionally Al, and a tetravalent element Y other than Si, which is one or more of Sn, Ti, Zr, and Ge, wherein in the framework structure of the zeolitic material in (ii), the molar ratio Al:Si is in the range of from 0:1 to 0.001:1, and wherein the framework structure of the zeolitic material in (ii) has framework type BEA, MFI, MWW, or a mixed structure thereof.

2. The process of claim 1, wherein Y is one or more of Sn and Zr.

3. The process of claim 1, where the framework structure of the zeolitic material in (ii) comprises Y in an amount of from 1 to 20 weight-%, based on the total weight of the zeolitic material.

4. The process of claim 1, wherein the framework structure of the zeolitic material in (ii) does not comprise a trivalent element X other than optionally Al.

5. The process of claim 1, wherein at least 99 weight-% of the framework structure of the zeolitic material in (ii) consist of Si, Y, O and H.

6. The process of claim 1, wherein the framework structure of the zeolitic material in (ii) has framework type BEA.

7. The process of claim 6, wherein the zeolitic material comprises Sn in an amount in the range of from 2 to 20 weight-% based on the total weight of the zeolitic material.

8. The process of claim 1, wherein the formaldehyde in (i) is one or more of aqueous formaldehyde, trioxane and paraformaldehyde.

9. The process of claim 1, wherein in the mixture provided in (i), the molar ratio of the compound of formula (I) relative to the formaldehyde, calculated as CH.sub.2O, is in the range from 1:1 to 12:1.

10. The process of claim 1, wherein the mixture in provided in (i) additionally comprises a solvent.

11. The process of claim 1, wherein the contacting in (ii) is effected at a temperature of the mixture in the range of front 60 to 150 C.

12. The process of claim 1, wherein the contacting in (ii) is carried out in the liquid phase.

13. The process of claim 1, wherein R.sub.1 and R.sub.2 are each H and R.sub.3 is C.sub.1-C.sub.10 alkyl.

14. The process of claim 1, wherein Y is one or more of Sn, Ti, Zr, and Ge.

15. The process of claim 1, wherein Y is Sn.

16. The process of claim 1, where the framework structure of the zeolitic material in (ii) comprises Y in an amount of from 4 to 16 weight-%, based on the total weight of the zeolitic material.

17. The process of claim 1, wherein at least 99.99 weight-% of the framework structure of the zeolitic material in (ii) consist of Si, Y, O and H.

Description

EXAMPLES

Reference Example 1: Analytical Methods

Reference Example 1.1: Analysis of the Mixture Obtained in (II): Compound of Formula (II) and Formaldehyde

(1) The product of formula (II) was quantified by Gas Chromatography weight-% calibrated:

(2) GC-system: Agilent 5890 Series II;

(3) GC-Column: DB-WAX (30 m (length), 0.32 mm (ID), 0.25 micrometer (film));

(4) Temperature program: 35 C. for 7 minutes, 35 C. to 230 C. at 6 K/min.

(5) The unreacted free formaldehyde in the mixture obtained in (ii) was photometrically quantified according the following reaction of formaldehyde with acetylacetone and NH.sub.4.sup.+:
CH.sub.2O+2C.sub.5H.sub.8O.sub.2+NH.sub.4.sup.+.fwdarw.3,5-diacetyl-1,4-dihydrolutidine+3H.sub.2O.

(6) The concentration of the then obtained 3,5-diacetyl-1,4-dihydrolutidine is equivalent to the concentration of formaldehyde and was measured at a wavelength of 412 nm.

Reference Example 1.2: Determination of the Crystallinity of the Zeolitic Material of Reference Example 2.1

(7) The crystallinity of the zeolitic materials of Reference Example 2.1 was determined by XRD analysis using the EVA method as described in the User Manual DIFFRAC.EVA Version 3, page 105, from Bruker AXS GmbH, Karlsruhe.

(8) The respective data were collected on a standard Bruker D8 Advance Diffractometer Series II using a Sol-X detector, from 2 to 50 2theta, using variable slits (V20), a step size of 0.02 2theta and a scan speed of 2.4 s/step. Default parameters were used for estimating the background/amorphous content (Curvature=1, Threshold=1).

Reference Example 1.3: Determination of the Water Adsorption of the Zeolitic Material

(9) Water adsorption/desorption isotherms were performed on a VTI SA instrument from TA Instruments following a step-isotherm program. The experiment consisted of a run or a series of runs performed on a sample material that has been placed on the microbalance pan inside of the instrument. Before the measurement was started, the residual moisture of the sample was removed by heating the sample to 100 C. (heating ramp of 5 C./min) and holding it for 6 h under a nitrogen flow. After the drying program, the temperature in the cell was decreased to 25 C. and kept isothermal during the measurement. The microbalance was calibrated, and the weight of the dried sample was balanced (maximum mass deviation 0.01 weight-%). Water uptake by the sample was measured as the increase in weight over that of the dry sample. First, as adsorption curve was measured by increasing the relative humidity (RH) (expressed as weight-% water in the atmosphere inside of the cell) to which the sample was exposed and measuring the water uptake by the sample as equilibrium. The RH was increased with a step of 10 weight-% from 5% to 85% and at each step the system controlled the RH and monitored the sample weight until reaching the equilibrium conditions after the sample was exposed from 85 weight-% to 5 weight-% with a step of 10% and the change in the weight of the sample (water uptake) was monitored and recorded.

Reference Example 1.4: Temperature Programmed Desorption of Ammonia (NH.SUB.3.-TPD)

(10) The temperature-programmed desorption of ammonia (NH.sub.3-TPD) was conducted in an automated chemisorption analysis unit (Micromeritics AutoChem II 2920) having a thermal conductivity detector. Continuous analysis of the desorbed species was accomplished using an online mass spectrometer (OmniStar QMG200 from Pfeiffer Vacuum). The sample (0.1 g) was introduced into a quartz tube and analysed using the program described below. The temperature was measured by means of an Ni/Cr/Ni thermocouple immediately above the sample in the quartz tube. For the analyses, He of purity 5.0 was used. Before any measurement, a blank sample was analysed for calibration. 1. Preparation: Commencement of recording; one measurement per second. Wait for 10 minutes at 25 C. and a He flow rate of 30 cm.sup.3/min (room temperature (about 25 C.) and 1 atm); heat up to 600 C. at a heating rate of 20 K/min; hold for 10 minutes. Cool down under a He flow (30 cm.sup.3/min) to 100 C. at a cooling rate of 20 K/min (furnace ramp temperature); Cool down under a He flow (30 cm.sup.3/min) to 100 C. at a cooling rate of 3 K/min (sample ramp temperature). 2. Saturation with NH.sub.3: Commencement of recording; one measurement per second. Change the gas flow to a mixture of 10% NH.sub.3 in He (75 cm.sup.3/min; 100 C. and 1 atm) at 100 C.; hold for 30 minutes. 3. Removal of the excess: Commencement of recording; one measurement per second. Change the gas flow to a He flow of 75 cm.sup.3/min (100 C. and 1 atm) at 100 C.; hold for 60 min. 4. NH.sub.3-TPD: Commencement of recording; one measurement per second. Heat up under a He flow (flow rate: 30 cm.sup.3/min) to 600 C. at a heating rate of 10 K/min; hold for 30 minutes. 5. End of measurement.

(11) Desorbed ammonia was measured by means of the online mass spectrometer, which demonstrates that the signal from the thermal conductivity detector was caused by desorbed ammonia. This involved utilizing the m/z=16 signal from ammonia in order to monitor the desorption of the ammonia. The amount of ammonia adsorbed (mmol/g of sample) was ascertained by means of the Micromeritics software through integration of the TPD signal with a horizontal baseline.

Reference Example 2: Preparation of Zeolitic Materials

(12) 2.1 Preparation of a Zeolitic Material Having Framework Type BEA and Comprising Sn (Sn-BEA)

(13) a) Preparation of Sn-BEA-Zeolite Materials used:

(14) TABLE-US-00001 50 g Deboronated BEA-zeolite, spray dried (prepared according to Example 1(ii) of WO 2014/060259) 14.2 g Sn(OAc).sub.2 (tin(II)acetate) from Aldrich 50 g of deboronated BEA zeolite and 14.2 g Sn(OAc).sub.2 were combined in the laboratory mixer and were ground for 15 min. The obtained mixture was then calcined in a muffle furnace by raising the temperature at the rate of 2 K/min to 500 C. for 3 h. 55.5 g of the zeolite of a) were obtained.

(15) b) Acid Treatment Materials used:

(16) TABLE-US-00002 55 g Sn-BEA zeolite according to a) 1650 g HNO.sub.3 30% aqueous solution 761.5 g of a solution of 65% HNO.sub.3 were added to a stirred 2 L vessel charged with 888.5 g of deionized water. Under continuous stirring, 55 g of the zeolite according to a) were added to the mixture. The obtained suspension was heated to 100 C. and refluxed for 20 h. The suspension was then cooled, filtered and washed with distilled water until neutral pH (<100 microSiemens). The filtered zeolite was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 10 h followed by raising the temperature at the rate of 2 K/min to 550 C. for 10 h. 52.8 g of the zeolite of b) were obtained.

(17) c) Preparation of a Molding Materials used:

(18) TABLE-US-00003 60 g Sn-BEA zeolite of b) 17.37 g ZrOH(OAc).sub.3 (~10% ZrO.sub.2) from Aldrich 3 g Walocel Wolf Walsrode AG PUFAS Werk KG 53 mL DI water 60 g of Sn-BEA zeolite of b), 17.37 g of ZrOH(OAc).sub.3 and 3 g of Walocel were combined and mixed in a kneader. 53 mL of deionized water were then added to the mixture which was kneaded until combined. The total kneading time was 30 min. The obtained zeolite was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 6 h followed by raising the temperature at the rate of 2 K/min to 550 C. for 5 h under air. 52.8 g of the molding with a bulk density of 440 g/L were obtained.

(19) 2.2 Preparation of a Zeolitic Material Having Framework Type MFI and Comprising Zr (Zr-MFI)

(20) a) Preparation of Zeolite Materials used:

(21) TABLE-US-00004 568.75 g tetraethyl orthosilicate (TEOS) 30.87 g Zr(IV)propoxide (70% solution in 1-propanol) 500 g tetrapropylammonium hydroxide (TPAOH) 500 g DI water 30.87 g of Zr(IV) propoxide were added dropwise over 30 min to a vessel charged with 568.75 g of TEOS. 500 g of TPAOH and 500 g of distilled water were added to the mixture which was then stirred for an additional 1 h. 407 g of accrued alcohol were distilled off from the mixture at 95 C. The resulting mixture was then cooled to room temperature. The sol was then diluted with 407 g of DI water. The resulting mixture was then crystallized at 175 C. for 48 h. The sol was diluted 1:1 with distilled water and adjusted to pH 7.5 with 5% HNO.sub.3 solution. The solids were centrifuged. The resulting zeolite was dried at 110 C. for 24 h followed by calcination by raising the temperature at the rate of 2 K/min to 500 C. for 5 h. 128 g of the Zr-MFI zeolite of a) were obtained.

(22) b) Preparation of Molding Materials used:

(23) TABLE-US-00005 50 g Zr-MFI: zeolite according to a) 22.06 g 15% SiO.sub.2 on zeolite (Ludox AS-40) 2.5 g Walocel Wolf Walsrode AG PUFAS Werk KG 50 mL DI water 50 g of Zr-MFI according to a), 22.06 g of 15% SiO.sub.2 of zeolite and 2.5 g of Walocel were combined and mixed in a kneader for 10 min. 50 ml of distilled water were then added to the mixture which was kneaded until combined. The total kneading time was 30 min. The obtained zeolite was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 7 h followed by raising the temperature at the rate of 2 K/min to 500 C. for 2 h. 40.3 g of the molding with bulk density of 320 g/L were obtained.

(24) c) Water Treatment Materials used:

(25) TABLE-US-00006 30 g molding according to b) 600 mL DI water The molding was suspended in DI water and heated at 145 C. for 8 h. The suspension was filtered. The zeolite was then dried at 120 C. for 12 h and calcined by raising the temperature at the rate of 2 K/min to 450 C. for 2 h. 39.3 g of the molding with bulk density of 300 g/L were obtained.

(26) 2.3 Preparation of a Zeolitic Material Having Framework Type MFI and Comprising Sn and Ti (Sn-TiMFI)

(27) a) Preparation of Zeolite Materials used:

(28) TABLE-US-00007 575.5 g tetraethyl orthosilicate (TEOS) 1.6 g tin (IV) isopropoxide 12.0 g tetraethyl titanate (TETi) 505.9 g tetrapropylammonium hydroxide (TPAOH) 505.9 g DI water 575.5 g of (TEOS) and 1.6 g of Tin (IV) isopropoxide were stirred together in a vessel for 10 min. Under continuous stirring 12.0 g of TETi were added dropwise and the mixture was then stirred for another 20 min. 505.9 g of TPAOH and 505.9 g of DI water were added to the mixture which was then stirred for an additional 1 h. 369 g of accrued alcohol were distilled off from the mixture at 95 C. The resulting mixture was then cooled to the room temperature. The sol was then diluted with 369 g of purified water. The resulting mixture was then crystallized at 175 C. for 48 h. The sol was diluted 1:1 with DI water and adjusted to pH 7.5 with 10% HNO.sub.3 solution. The solid was filtered off and the resulting zeolite was dried at 110 C. for 24 h followed by calcination by raising the temperature at the rate of 2 K/min to 550 C. for 5 h. 168.4 g of the zeolite of a) were obtained.

(29) b) Preparation of the Molding Materials used:

(30) TABLE-US-00008 60 g SnTi-MFI according to a) 16.67 g (10% SiO.sub.2 on zeolite) Ludox AS-40 3 g Walocel (Wolf Walsrode AG PUFAS Werk KG) 40 mL DI water 60 g of the zeolite SnTi-MFI according to a), 16.67 g of Ludox and 3 g of Walocel were combined and mixed in a kneader for 10 min. 40 mL of purified water were then added to the mixture which was kneaded until combined. The total kneading time was 30 min. The obtained molding was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 7 h followed by raising the temperature at the rate of 2 K/min to 500 C. for 2 h. 47.2 g of the molding with bulk density of 525 g/L were obtained.

(31) 2.4 Preparation of a Zeolitic Material Having Framework Type MWW and Comprising Ga (Ga-MWW)

(32) a) Preparation of a Zeolite Materials used:

(33) TABLE-US-00009 40 g MWW zeolite prepared according to example 1 of WO 2014/060261 2 g Ga(OMe).sub.3 A laboratory mixer was prepared for the reaction by being purged with N.sub.2 for 30 min. Under N.sub.2 atmosphere 40 g of the zeolite and 2 g of Ga(OMe).sub.3 were combined in the prepared laboratory mixer and were ground for 5 min on a middle speed (speed 4). The obtained mixture was dried at 120 C. and then calcined in a muffle furnace by raising the temperature at the rate of 2 K/min to 500 C. for 5 h. 39.4 g of the zeolite of a) were obtained.

(34) b) Preparation of the Molding Materials used:

(35) TABLE-US-00010 30 g Ga-MWW zeolite according to a) 18.75 g (20% SiO2 on zeolite) Ludox AS-40 1.5 g Walocel (Wolf Walsrode AG PUFAS Werk KG) 65 mL DI water 30 g of Ga-MWW zeolite according to a), 18.75 g of 20% SiO.sub.2 on zeolite and 1.5 g of Walocel were combined and mixed in a kneader for 10 min. 65 ml of DI water were then added to the mixture which was kneaded until combined. The total kneading time was 60 min. The obtained zeolite was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 7 h followed by raising the temperature at the rate of 2 K/min to 500 C. for 2 h. 25.3 g of the molding with bulk density of 250 g/L were obtained.

(36) c) Water Treatment Materials used:

(37) TABLE-US-00011 20 g Ga-MWW zeolite according to b) 400 mL DI water The molding was suspended in DI water and heated at 145 C. for 8 h. The suspension was filtered. The zeolite was then dried at 120 C. for 12 h and calcined by raising the temperature at the rate of 2 K/min to 450 C. for 2 h. 20 g of the molding with a bulk density of 240 g/L were obtained.

(38) 2.5 Preparation of a Zeolitic Material Having Framework Type MFI and Comprising Ga (Ga-MFI)

(39) a) Preparation of a Zeolite Materials used:

(40) TABLE-US-00012 272 g Tetraethyl orthosilicate (TEOS) Solution 1:

(41) TABLE-US-00013 8.4 g Natrium hydroxide pellets 272 g DI water 106.1 g 40% tetrapropylammonium hydroxide Solution 2:

(42) TABLE-US-00014 6.7 g Ga(NO.sub.3).sub.3 xH.sub.2O 68 g DI water A 100 mL dropping funnel was charged with solution 1 and a 500 mL dropping funnel was charged with solution 2. Solution 1 and solution 2 were added dropwise at the same time to a vessel charged with 272 g of TEOS. After 10 min two phases were observed. After 20 min addition of solution 2 ended at 27 C. and 3 min after that the addition of solution 1 ended at 28 C. The resulting mixture was then stirred for 2 h. After additional 5 min a gel was formed. The temperature of the mixture rose to 40 C. in 35 min, and then was cooled off. An autoclave was charged with the gel and was heated at 180 C. for 72 h. The resulting solid was filtered with a black band filter and washed with DI water. The solid was dried overnight at room temperature. The resulting zeolite was then calcined by raising the temperature at a rate of 2 K/min to 540 C. and 10 h at 550 C. under air. 70 g of the zeolite of a) were obtained.

(43) b) Ion Exchange Materials used:

(44) TABLE-US-00015 585 g DI water 65 g 99% ammonium nitrate (NH.sub.4NO.sub.3) 65 g Ga-MFI according to a) 585 g of DI water and 65 g of 99% ammonium nitrate (NH.sub.4NO.sub.3) were combined to form a 10% solution. Under continuous stirring 65 g of the Ga-MFI zeolite according to a) were added to the mixture. The obtained mixture was heated to 80 C. and stirred for 2 h. The suspension was then cooled and stirring stopped. After settling, the supernatant solution was removed. A fresh ammonium nitrate solution (10%) was added to the remaining solids and the procedure was repeated. The suspension was then filtered off and washed with DI water. The filtered zeolite was dried at 120 C. for 4 h and then calcined at 500 for 5 h. The temperature program used was: 60 min to 120 C.; 240 min at 120 C.; 190 min to 500 C.; 300 min at 500 C. Air was used as medium. The ion exchange was repeated one more time. The zeolite was dried at 120 C. for 4 h and then calcined at 500 C. for 5 h. The temperature program used was: 60 min to 120 C.; 240 min at 120 C.; 190 min to 500; 300 min at 500 C.

(45) Air was used as medium. 61 g of the zeolite of b) were obtained.

(46) c) Preparation of Molding Materials used:

(47) TABLE-US-00016 40 g Ga-MFI zeolite according to b) 17.65 g (15% SiO.sub.2 on zeolite) Ludox AS-40 2 g Walocel (Wolf Walsrode AG PUFAS Werk KG) 29 mL DI water 40 g of Ga-MFI according to b), 17.65 g of (15% SiO.sub.2 on zeolite) and 2 g of Walocel were combined and mixed in a kneader for 10 min. 29 ml of DI water were then added to the mixture which was kneaded until combined. The total kneading time was 30 min. The obtained zeolite was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 7 h followed by raising the temperature at the rate of 2 K/min to 500 C. for 2 h. 34.2 g of the molding with bulk density of 410 g/L were obtained.

(48) d) Water Treatment Materials used:

(49) TABLE-US-00017 30 g the molding according to c) 600 mL DI water The molding was suspended in DI water and heated at 145 C. for 8 h. The suspension was filtered. The zeolite was then dried at 120 C. for 12 h and calcined by raising the temperature at the rate of 2 K/min to 450 C. for 2 h. 30.8 g of the molding with bulk density of 410 g/L were obtained.

(50) 2.6 Preparation of a Zeolitic Material Having Framework Type MFI/MEL and Comprising Fe and (Fe-MFI/MEL)

(51) a) Preparation of the Zeolite 273 kg sodium silicate were provided in a vessel. Under stirring at 100 rpm (rounds per minute), 252.8 kg of hexamethylenediamine solution (56.6 wt.-%) were added and the reactor temperature was raised to 50 C. To the resulting solution, a solution containing: 425 kg de-ionized water, 20.64 kg sulfuric acid (96 wt. %) and 31.1 kg Fe.sub.2(SO.sub.4).sub.3H.sub.2O was added. The resulting mixture was stirred at 162 rpm for 17 h. The finally obtained mixture was heated to 160 C. within 4 h under autogenous pressure and under stirring (30 rpm). The temperature of 160 C. was kept essentially constant for 94 h; during these 94 h, the mixture was stirred at 18 rpm. Subsequently, the mixture was cooled to a temperature of 40 C. within 2 h. After cooling the zeolite material was separated by filtration using a suction filter. The filter cake was washed with de-ionized water until the washing water had a conductivity of less than 300 microSiemens/cm. The filter cake obtained by the separation described above was dried in a static oven at 120 C. for 10 h. The dried material was then subjected to calcination at 500 C. in a static oven for 5 h.

(52) b) Preparation of the Molding Materials used:

(53) TABLE-US-00018 60 g the zeolite according to a) 26.47 g (15% SiO.sub.2 on zeolite) Ludox AS-40 3 g Walocel Wolf Walsrode AG PUFAS Werk KG 77 mL DI water 60 g of the zeolite according to a), 26.47 g of 15% SiO.sub.2 on zeolite and 3 g of Walocel were combined and mixed in a kneader for 10 min. 77 mL of DI water were then added to the mixture which was kneaded until combined. The total kneading time was 30 min. The obtained zeolite was then calcined in the muffle furnace by raising the temperature at the rate of 3 K/min to 120 C. for 7 h followed by raising the temperature at the rate of 2 K/min to 500 C. for 2 h. 54 g of the molding with bulk density of 320 g/L were obtained.

(54) c) Water Treatment Materials used:

(55) TABLE-US-00019 30 g molding according to b) 600 mL DI water The molding of b) was suspended in DI water and heated at 145 C. for 8 h. The suspension was filtered. The zeolite was then dried at 120 C. for 12 h and calcined by raising the temperature at the rate of 2 K/min to 450 for 2 h. 33.4 g of the molding with bulk density of 330 g/L were obtained.

(56) 2.7 Preparation of a Zeolitic Material ZSM-5 Having Framework Type MFI A ZSM-5 catalyst commercially available was water treated after shaping to impart mechanical strength. The NH3-TPD analysis of this material showed Brnsted acidity related to NH3-desorption above 250 C. The reaction for the preparation 3-methyl-3-buten-1-ol carried out with this catalyst was seen to be totally unselective. Selectivity is defined in this context as the molar amount of 3-methyl-3-buten-1-ol relative to the molar amount of formaldehyde brought into contact with the condensation catalyst.

Examples: Preparation of 3-methyl-3-buten-1-ol

E1. Using the Zeolitic Material Sn-BEA According to Reference Example 2.1 as Catalytically Active Material

(57) 55 g of an aqueous solution of formaldehyde (FA) (49 weight-%) were dissolved in 445 g of tert-butanol. A formaldehyde solution (5.39 weight-%) was obtained. This solution was dosed to an isothermal tubular reactor at 32 g/h (0.05 mol FA/h). The isobutene flask was pressurized with helium (to liquefy the gas) and pumped into the reactor at 31.3 g/h (0.55 mol/h). The two streams were pressurized to 20 bar and tempered to 100 C. before entering the reactor. The tubular reactor had a length of 110 cm and contained 10.85 g of a Sn-BEA catalyst according to Reference Example 2.1. The reactor was operated at 100 C. and at a constant pressure of 20 bar. The residence time was of about 15.67 min. The reaction was run for 48 h, and 4 samples were analysed during this time. After the reaction, the yield for 3-methyl-3-buten-1-ol based on the formaldehyde conversion was calculated with weight calibrated Gas Chromatography according to Reference Example 1.1. The unreacted formaldehyde was photometrically quantified according to Reference Example 1.1. The yield (Y), the selectivity (S) and the conversion (C) obtained are shown in Table 1 below.

(58) TABLE-US-00020 TABLE 1 After 6 h After 24 h After 30 h After 48 h Catalyst Y% S% C% Y% S% C% Y% S% C% Y% S% C% SnBea 70 71 99 72 72 100 73 73 99 71 72 99 After 54 h After 72 h After 78 h After 96 h After 102 h Y% S% C% Y% S% C% Y% S% C% Y% S% C% Y% S% C% 67 68 99 69 69 99 67 68 99 69 70 99 67 68 99

E2. Using the Zeolitic Material Zr-MFI According to Reference Example 2.2 as Catalytically Active Material

(59) The protocol of Example E1 was repeated using Zr-MFI zeolite as catalyst. The tubular reactor was filled with 10.08 g of the Zr-MFI zeolite. The residence time was of 15.5 min. The reaction was run for 100 h and 9 samples were analysed during this time. After the reaction, the yield for 3-methyl-3-buten-1-ol based on the formaldehyde conversion was calculated with weight calibrated Gas Chromatography according to Reference Example 1.1. The unreacted formaldehyde was photometrically quantified according to Reference Example 1.1. The yield (Y), the selectivity (S) and the conversion (C) obtained are shown in Table 2 below.

(60) TABLE-US-00021 TABLE 2 After 6 h After 24 h After 30 h After 48 h Catalyst Y% S% C% Y% S% C% Y% S% C% Y% S% C% ZrMFI 43 43 100 46 49 95 47 51 93 44 48 91 After 54 h After 72 h After 78 h After 96 h After 102 h Y% S% C% Y% S% C% Y% S% C% Y% S% C% Y% S% C% 44 49 89 41 47 88 42 49 87 40 47 86 42 51 83

E3. Using the Zeolitic Material SnTI-MFI According to Reference Example 2.3 as Catalytically Active Material

(61) The protocol of example E1 was repeated using SnTi-MFI zeolite as catalyst. The tubular reactor was filled with 10.15 g of the SnTi-MFI zeolite. The residence time was of 155 min. The reaction was run for 100 h and 9 samples were analysed during this time. After the reaction, the yield for 3-methyl-3-buten-1-ol based on formaldehyde conversion was calculated with weight calibrated Gas Chromatography according to Reference example 1.1. The unreacted formaldehyde was photometrically quantified according to Reference Example 1.1. The yield (Y), the selectivity (S) and the conversion (C) obtained are shown in Table 3 below.

(62) TABLE-US-00022 TABLE 3 After 6 h After 24 h After 30 h Catalyst Y% S% C% Y% S% C% Y% S% C% SnTi-MFI 38 38 100 45 45 100 49 49 100 After 48 h After 52 h Y% Y% Y% Y% S% C% 47 47 47 40 40 100

Comparative Examples: Preparation of 3-methyl-3-buten-1-ol

CE1. Using the Zeolitic Material Ga-MWW According to Reference Example 2.4 as Catalytically Active Material

(63) The protocol of Example E1 was repeated using Ga-MWW zeolite as catalyst. The tubular reactor was filled with 10.10 g of the Ga-MWW zeolite. The residence time was of 15.5 min. The reaction was run for 28 h and 3 samples were analysed during this time. After the reaction, the yield for 3-methyl-3-buten-1-ol based on formaldehyde conversion was calculated with weight calibrated gas chromatography according to Reference Example 1.1. The unreacted formaldehyde was photometrically quantified according to Reference Example 1.1. The yield (Y), the selectivity (S) and the conversion (C) obtained are shown in Table 4 below.

(64) TABLE-US-00023 TABLE 4 After 6 h After 24 h After 28 h Catalyst Y% S% C% Y% S% C% Y% S% C% Ga-MWW 7 7 100 9 9 100 10 10 100

CE2. Using the Zeolitic Material Ga-MFI According to Reference Example 2.5 as Catalytically Active Material

(65) The protocol of Example E1 was repeated using Ga-MFI zeolite as catalyst. The tubular reactor was filled with 10.20 g of the Ga-MFI zeolite. The residence time was of 15.5 min. The reaction was run for 39 h and 5 samples were analysed during this time. After the reaction, the yield for 3-methyl-3-buten-1-ol based on formaldehyde conversion was calculated with weight calibrated Gas Chromatography according to Reference Example 1.1. The unreacted formaldehyde was photometrically quantified according to Reference Example 1.1. The yield (Y), the selectivity (S) and the conversion (C) obtained are reported in Table 5 below.

(66) TABLE-US-00024 TABLE 5 After 6 h After 24 h After 30 h After 33 h After 39 h Catalyst Y% S% C% Y% S% C% Y% S% C% Y% S% C% Y% S% C% Ga-MFI 29 30 100 35 35 98 34 34 99 28 28 100 34 34 99

CE3. Using the Zeolitic Material Fe-MFI/MEL According to Reference Example 2.6 as Catalytically Active Material

(67) The protocol of Example E1 was repeated using FeMFI/MEL zeolite as catalyst. This time the tubular reactor was filled with 10.10 g of the Fe MFI/MEL zeolite. The residence time was of 15.7 min. The reaction was run for 30 h and 3 samples were analysed during this time. After the reaction, the yield for 3-methyl-3-buten-1-ol based on formaldehyde conversion was calculated with weight calibrated Gas Chromatography according to Reference Example 1.1. The unreacted formaldehyde was photometrically quantified according to Reference Example 1.1. The yield (Y), the selectivity (S) and the conversion (C) obtained are reported in Table 6 below.

(68) TABLE-US-00025 TABLE 6 After 6 h After 24 h After 28 h Catalyst Y% S% C% Y% S% C% Y% S% C% FeMFI/MEL 25 25 100 15 15 100 10 10 100

(69) Results

(70) As can be taken from the results above, the zeolitic materials of inventive examples E1 to E3 show a higher yield compared to all the zeolitic material of comparative examples CE1 to CE3 at a temperature of 100 C. In addition, the zeolitic materials of inventive examples E1 to E3 exhibit a higher selectivity at a temperature of 100 C. compared to the zeolitic material of comparative examples CE1 to CE3.

CITED LITERATURE

(71) WO 2015/067654 A WO 2014/060261 A WO 2014/060259 A Komatsu et al., Porous Material in Environmentally Friendly Processes, vol. 125, 1999, pages 507-514 US 2012059177 A WO 2011/154330 A WO 2011/147919 A US 2011054083 A Zhaoyang et al., Journal of Industrial and Engineering Chemistry, vol. 20, 2014, pages 4146-4151 Fernandes et al., Tetrahedron Letters, vol. 44, 2003, pages 1275-1278