WO2021222052A1

WO2021222052A1 - Copper catalyst and method of making same

Info

Publication number: WO2021222052A1
Application number: PCT/US2021/029050
Authority: WO
Inventors: Huan Wang; Ai Ling LV; Diana Carolina GALEANO NUNEZ; Mario Soorholtz
Original assignee: BASF Corp
Current assignee: BASF Corp
Priority date: 2020-04-28
Filing date: 2021-04-26
Publication date: 2021-11-04
Anticipated expiration: 2022-10-28
Also published as: CN115485061A

Abstract

The present invention is related to a catalytic composition and a method for the production of 1,4-butynediol by catalytic ethynylation of formaldehyde. In one embodiment the invention provides fo a catalytic composition comprising from 20% to 80% by weight of Cu, calculated as CuO; from 0.5% to 15% by weight of Bi, calculated as Bi2O3; from 6.6% to 40% by weight of Ca, calculated as CaO; and from 0% to 30% by weight of Si, calculated as SiO2.

Description

COPPER CATALYST AND METHOD OF MAKING SAME

FIELD OF THE INVENTION

The present invention is generally related to a catalytic composition and a method for the production of 1 ,4-butynedioi by catalytic ethynyiation of formaldehyde, the said method is known as the Reppe reaction.

BACKGROUND OF THE INVENTION

1 ,4-butynediol (BYD), is an important organic compound intermediate and forms derivatives with various chemicals. In recent years, high growth of the hydrogenation product 1,4-butanedioi (BDO) and its downstream products, i.e., gamma-butyro!aclone (GBL), tetrahydrofuran (THF), polybutylene terephthaiate (PBT) and polyurethane (PU), raises an increase in demand of 1 ,4-butynedioi. Industrial process to produce 1,4-butynedio! is mainly by reaction of formaldehyde and acetylene via coal chemical industry. There is abundant coal resource which makes the production of via coal-chemistry route has unique advantages and much lower cost.

Reppe invented the synthesis of 1 ,4-butynedioi by use of formaldehyde and acetylene as raw material in the 1940s. it was conducted in a fixed-bed reactor under high pressure catalyzed by acetyiide of noble metal (especially copper), which increases operation risk of acetylene and copper acetyiide. Since the 1970s, new catalysts with small particle size and well activity and improved techniques for production of 1 ,4-butynediol has been invented. It was conducted in a siurry-phase reactor, which decreases operation pressure and risk of explosion. For example, E. V. Hort (GAF Corporation) U.S. Pat. No. 3920759 (1975), discloses a process patent for producing 1,4-butynedioi using a copper oxide containing catalyst precursor with about 5 to about 20% copper, 0 to about 3% bismuth, and a magnesium silicate carrier, importantly, the Hort patent teaches that the catalyst is prepared via impregnation of the magnesium silicate carrier with a solution of copper nitrate and bismuth nitrate solution.

According to U.S. Pat. No. 3920759, the synthesis is conducted with the catalyst, impregnated on an inert powdered carrier, such as magnesium silicate, silica, carbon, alumina and so on, preferably magnesium silicate, at atmospheric pressure with complete safety in as much as any explosive tendency of the overall system is eliminated by the inert carrier. In order to suppress formation of by-product cuprene, additives of bismuth oxide is used. The active catalyst precursor is formed by addition of copper and bismuth salt solution onto the carrier, drying and calcination.

Based on to U.S. Pat. No. 9006129, one catalyst for Reppe reaction is prepared by precipitation of copper and bismuth nitrates by use of sodium hydroxide in the presence of magnesium silicate carrier, followed by drying and calcination to form coated carrier particles with copper oxide and bismuth oxide. However, it has been found that the magnesium silicate is specifically in the form of small spheres with a particle size dso of about 15 microns, which is dramatically costly than conventional carrier materials. Besides, the catalytic activity and fi!terability of above catalyst still need to be improved to some extent for long-term application in production scale.

US Pat. Appl. No. 2018/0236439 A1 discloses a process of forming an ethynyiation catalyst. The process includes providing an aqueous slurry comprising water, a copper-containing material, a bismuth-containing material, a structural material, and a binder; spray-drying the slurry to form particles; and calcining the particles to form the ethynyiation catalyst.

SUGARY OF THE INVENTION Catalytic activity and filtration speed of the currently commercial catalysts should be improved to satisfy the potential demand for the future. The object of this invention is to provide a Reppe reaction catalytic composition with improved catalytic activity and filterabi!ity. in one aspect, a catalytic composition is provided, wherein the catalytic composition comprises from 20% to 80% by weight of Cu, calculated as CuO; from 0.5% to 15% by weight of Bi, calculated as Bi₂O₃; from 6.6% to 40% by weight of Ca, calculated as CaO; and from 0% to 30% by weight of Si, calculated as SiO₂.

In another aspect, a process for producing the catalytic composition described above is provided, wherein the process comprises 1) precipitation of a copper-containing aqueous solution with precipitation agent, on a particulate carrier; 2) drying and calcining the treated particulate carrier to form the catalytic composition; wherein the particulate carrier comprises a calcium source.

In another aspect, a process for using the catalytic composition described above for hydrogenation, dehydrogenation, hydrogeno!ysis, or ethynyiation is provided.

The catalytic composition prepared in this invention has higher catalytic activity and higher filtration rate compared to commercial magnesium silicate supported catalysts.

DETAILED DESCRIPTION OF THE HNVENTHON

Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the foliowing description. The invention is capable of other embodiments and of being practiced or being carried out in various ways.

With respect to the terms used in this disclosure, the following definitions are provided. Throughout the description, including the claims, the term "comprising one" or

"comprising a" should be understood as being synonymous with the term "comprising at least one", unless otherwise specified, and "between" or “to” should be understood as being inclusive of the limits.

The terms “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

The term “and/or” includes the meanings “and”, “or” and also all the other possible combinations of the elements connected to this term.

All percentages and ratios are mentioned by weight unless otherwise Indicated.

The catalytic activity of current commercial catalyst for Reppe reaction may not satisfy the increasing demand of 1 ,4-butynedioi in recent years. Meanwhile, the filtration rate of spent catalyst largely decreases after long-term operation. This may arise severe problem in actual production because a filter is used for separation of spent catalysts and reaction products, where some of spent catalysts are recycled, mixed with fresh catalyst and fed back into reactors. Therefore, the filtration rate of spent catalysts is critical to the recycling efficiency.

Thus, according to one aspect of the invention, provided is a catalytic composition comprising from 20% to 80%, preferably from 30% to 70%, including 40, 45, 50, 55, 80 and 85%, by weight of Cu, calculated as CuO; from 6.6% to 40%, preferably from 6.9% to 30%, including 9, 12, 15, 18, 20, 23, 25 and 27%, by weight of Ca, calculated as CaO; from 0.5% to 15%, preferably from 1% to 10%, more preferably from 1.5% to 5% including 2, 2.5, 3, 3.5, 4 and 4.5%, by weight of Bi, calculated as Bi₂O₃; and from 0% to 30%, preferably from 0% to 20% including 5, 10 and 15%, by weight of Si, calculated as SiO₂. In one or more embodiments, the catalytic composition further comprises from 0.01% to 30%, preferably from 0.1% to 25%, including 0.5, 2, 4, 6, 8, 10, 12, 15, 18, 20 and 22%, by weight of Mg, calculated as MgO. in one or more embodiments, the catalytic composition has a specific BET surface area after 2hr calcination in air at 30G°C, characterized by 77K nitrogen sorption, in the range of 1 to 45 m²·g^-1, preferably in the range of 1.5 to 20 m²·g^-1.

"BET surface area" has its usual meaning of referring to the Brunauer-Emmett-Tel!er method for determining specific surface area by N₂ adsorption.

Another aspect Includes methods for producing the catalytic composition described above, wherein the methods comprise steps of: 1) precipitation of an acidic copper-containing aqueous solution with precipitation agent, on a particulate carrier; and

2) drying the treated particulate carrier and calcining at 300 to 800 °C to form the catalytic composition; wherein the particulate carrier comprises a calcium source.

A type of the alkaline aqueous solution used as the precipitation agent is not particularly limited, but inorganic alkalis such as aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide and ammonium hydroxide, and the mixture thereof are generally used.

As used herein, the term "mixture" or "combination" refers, but is not limited to, a combination in any physical or chemical form, e.g., blend, solution, suspension, alloy, composite, or the like.

With reference to a copper source, typical copper sources may include, but not limited to, copper acetate, copper chloride, copper phosphate, copper pyrophosphate, copper nitrate, copper ammonium sulfate, copper albuminate, copper sulfate, copper gluconate, copper lactate, copper saccharate, copper fructate, copper dextrate, and the mixture thereof.

With reference to a bismuth source, typical bismuth sources may include, but not limited to bismuth chloride, bismuth oxychloride, bismuth bromide, bismuth silicate, bismuth hydroxide, bismuth trioxide, bismuth nitrate, bismuth subnitrate, bismuth oxycarbonate, and the mixture thereof.

With reference to a calcium source, typical calcium sources may include, but are not limited to. calcium chloride, calcium hydroxide, calcium carbonate, calcium bicarbonate, calcium nitrate, calcium sulfate, calcium silicate, calcium chloride, calcium chloride, calcium formate, calcium acetate, calcium gluconate, calcium ascorbate, calcium lactate, calcium giycinate, calcium magnesium carbonate, calcium magnesium silicate, and the mixture thereof.

With reference to a magnesium source, typical magnesium sources may include, but are not limited to magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium silicate, calcium magnesium carbonate, calcium magnesium silicate, magnesium a!uminate, aluminum magnesium hydroxide, aluminum magnesium oxide, and the mixture thereof.

With reference to a silica source, typical silica sources may include, but are not limited to silica, clay, talc, kaolin, pyrophyllite, bentonite, magnesium silicate, calcium silicate, magnesium calcium silicate, aluminum silicate, aluminum silicate hydrate, calcium aluminum silicate, calcium silicate hydrate, and the mixture thereof.

Other aspects include methods for using the catalytic composition described above for hydrogenation, dehydrogenation, hydrogenoiysis, or ethynylation.

Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein.

Preparation of the Catalyst

The particulate carrier generally will have an average diameter of from about 5 to 50 microns, preferably with d₅₀ from about 10 to 15 microns. The particulate carrier is first added to water in a precipitation vessel. An acidic solution is made up of a mixture of copper-containing and bismuth-containing salts in a separate vessel. A basic solution is made up of sodium hydroxide in a separate vessel. The temperature of the solution in the precipitation vessel is set at the precipitation temperature which is held constant throughout the precipitation process with a value anywhere from about 40°C to about 90°C. The acid mixture and the sodium hydroxide solution are simultaneously added to the vessel containing water and the calcium-containing particulate carrier. The precipitation is carried out at a constant pH of about 8 to about 10. During precipitation, the flow of the acid solution is kept constant while the flow of the NaOH solution is adjusted to keep the precipitation pH constant The time of precipitation may be anywhere from 15 mins to 120 mins. Usually the time is about 80 mins to about 90 mins. After the precipitation step, the precipitate may be aged for a short time, about 15 mins to about 120 mins. Afterwards, the precipitate is filtered, washed, and dried. The dried material is calcined in air. The calcination temperature may vary between about 300°C to about 800°C, 400, 500, 600, and 700°C included.

Catalyst Composition After calcination the powdered, calcined catalyst material contains about 20 wt% to about 80 wt% copper oxide, and about 0.5 wt% to about 15 wt% bismuth oxide and about 7 wt% to about 40 wt% calcium calculated as calcium oxide. Sodium levels (as sodium oxide) are typically less than about 2 wt%. The balance of the powdered, calcined catalyst material is mostly a variety of oxides, carbonates, silicates and the mixture thereof depending on the specific particulate carrier used. For example, calcium carbonate contains the Ca, calcium silicate contains the both Ca and Si, and dolomite contains the both Mg and Ca. Impurities in small amounts such as alumina may be present.

Catalytic Performance Testing of the Catalyst

By use of identical testing conditions according to U.S. Pat. No. 9006129, the active catalyst is preferably generated by means of the introduction of the acetylene into the formaldehyde-catalyst reaction medium. In the first reactor, the calcined catalyst is mixed with formaldehyde aqueous solution. The pH of the aqueous medium is adjusted to the range of 7.0 to 10.0, and preferably 8.0. The control of pH is to suppress the formation of formic acid, which will react with copper compound and raise loss of copper due to leaching into solution. Activation of the catalyst is conducted after acetylene stream is introduced and the reactor is heated from room temperature to about 80°C. The activation process generally requires 5 hours.

Afterwards, the slurry was removed, centrifuged, and decanted, ieaving wet catalyst ready for activity testing. In the second reactor, a certain amount of wet catalyst is mixed with formaldehyde aqueous solution. Acetylene stream is then introduced with partial pressure generally from 0.5 to 1.9 atmospheres, preferably 1.0 atmosphere, catalyst will be present in amounts of about 1 to 20 weight parts per 100 weight parts of formaldehyde aqueous medium. The reactor is heated from room temperature to about 80°C. The reaction process generally requires 5 hours and the pH of aqueous medium after reaction is about 5.0. The product mixture is analyzed by gas chromatography in which butynediol (primary product) and propargyl alcohol (product intermediate) were quantified and the activity of cataiyst is determined. A sodium sulfite titration method is used to determine the amount of formaldehyde remaining in the product and overall formaldehyde conversion is thus calculated. Testing of the Catalyst

For ethynylation process in plant, a filter is used for separation of spent catalysts and reaction products. In this way, spent catalysts are recycled, mixed with fresh catalyst and fed back into reactors. Therefore, the filtration speed of spent catalysts is critical to the recycling efficiency. The filtration rate is tested for the catalyst after attrition: about 4g of fresh catalyst is added to 40mL Dl H20 and stirred at room temperature for a sufficiently long time. Afterwards, the slurry Is filtered, and the time used for filtration is recorded to calculate the filtration rate accordingly.

Through above performance evaluation procedures, the novel catalyst prepared in this invention has comparable and even higher catalytic activity and filterability than the commercial catalyst for production of 1,4-butynediol.

Embodiments

The invention will be more specifically described and explained by means of the following embodiments, which are not to be considered as limiting but only illustrative of the invention.

1. A catalytic composition comprising from 20% to 80% by weight of Cu, calculated as CuO; from 0.5% to 15% by weight of Bi, calculated as Bi₂O₃; from 6.6% to 40% by weight of Ca, calculated as CaO; and from 0% to 30% by weight of Si, calculated as SiO₂. 2. The catalytic composition according to embodiment 1, wherein the catalytic composition further comprises from 0.01% to 30% by weight of Mg, calculated as MgO.

3. The catalytic composition according to embodiments 1 or 2, wherein the catalytic composition further comprises from 1% to 10% by weight of Bi, calculated as Bi₂O₃.

4. The catalytic composition according to any one of embodiments 1 to 3, wherein the catalytic composition comprises from 30% to 70% by weight of Cu, calculated as CuO.

5. The catalytic composition according to any one of embodiments 1 to 4, wherein the catalytic composition comprises from 6.9% to 30% by weight of Ca, calculated as CaO.

8. The catalytic composition according to any one of embodiments 1 to 5, wherein the catalytic composition comprises from 0% to 20% by weight of Si, calculated as SiO₂. 7. The catalytic composition according to any one of embodiments 1 to 6, wherein the catalytic composition comprises from 0.1% to 25% by weight of Mg, calculated as MgO.

8. The catalytic composition according to any one of embodiments 1 to 7, wherein the catalytic composition comprises from 1.5% to 5% by weight of Bi, calculated as Bi₂O₃.

9. The catalytic composition according to any one of embodiments 1 to 8, wherein the catalytic composition has a specific BET surface area after 2hr calcination in air at 30G°C, characterized by 77K nitrogen sorption, in the range of 1 to 45 m²·g^-1, or in the range of 1.5 to 20 m²·g^-1.

10. A process for producing a catalytic composition according to any one of embodiments 1 to 9 comprising: 1) precipitation of an acidic copper-containing aqueous solution with precipitation agent, on a particulate carrier; and

2) drying the treated particulate carrier and calcining at 300 to 800 °C to form the catalytic composition; wherein the particulate carrier comprises a calcium source. 11. The process according to embodiment 10, wherein the calcium source is selected from the group consisting of calcium chloride, calcium hydroxide, calcium carbonate, calcium bicarbonate, calcium nitrate, calcium sulfate, calcium silicate, calcium chloride, calcium chloride, calcium formate, calcium acetate, calcium gluconate, calcium ascorbate, calcium lactate, calcium glycinate, calcium magnesium carbonate, calcium magnesium silicate, and the mixture thereof.

12. A process for using the catalytic composition according to any one of embodiments 1 to 9 for hydrogenation, dehydrogenation, hydrogenolysis, or ethynylation.

EXAMPLE

The invention will be more specifically described and explained by means of the following examples, which are not to be considered as limiting but only illustrative of the invention. All parts and proportions therein as well as in the appended claims are by weight unless otherwise specified.

Example 1

Dolomite as the particulate carrier is added into water to obtain a 25wt% slurry. Copper nitrate (70wt% Cu/dolomite) and bismuth nitrate (7wt% Bi/Cu) solution are precipitated with 15wt% sodium hydroxide solution onto the particulate carrier. After the precipitation step, the precipitate was aged at 35°C for 10 mins. Afterwards, the precipitate was filtered, dried and calcined at 400°C. The obtained catalyst shows a composition comprising 51.1wt% CuO, 3.0wt% B1₂O₃, 16.2wt% CaO, 8.0wt% MgO and 0.3wt% SiO₂. Examples 2 to 11, and Comparative Example

As shown in Table 1, Examples 2 to 11 and Comparative Example were prepared as the same procedure described above for Example 1 , but with different particulate carriers. Table 1 Catalyst component data

Example 12 Reaction testing procedure

Testing was carried out in two steps. First the catalyst was activated to form the active copper acetyiide on the surface of catalyst. It was then transferred to the reaction vessel. Detailed procedure is shown as following. The activation was conducted in the reactor containing 100mL formalin (37wt% formaldehyde aqueous solution). 1.5M sodium hydroxide solution was added to formalin to adjust initial pH to about 8.5 and 15 g of catalyst was then added to formalin after the adjust of pH. Inertization of the reactor was conducted by purging nitrogen and then gas flow was exchanged to acetylene with 8QmL/min. Start stirring at controlled pH of 8.0 and start heating up to 80°C. The reaction was kept for 5 hours. Afterwards, the reactor was cooled down to room temperature under gas flow of acetylene. Nitrogen was purged into reactor for inertization and the slurry was removed, centrifuged, and decanted, leaving wet catalyst ready for activity testing. 0.8 g (dry basis) of catalyst was added into reactor with formaldehyde aqueous solution. Similarly, the initial pH of formalin was adjusted to 8.0 by sodium hydroxide solution. The flow rate of acetylene was kept constant at 50 mL/min and the reaction temperature was 80°C. After 5 hours, the reactor was cooled down under gas flow of acetylene followed by purging of nitrogen for inertization. The slurry was removed and centrifuged. The product mixture is analyzed by gas chromatography in which butynedioi and propargyl alcohol were quantified. A sodium sulfite titration method is used to determine the amount of formaldehyde remaining in the product. Thereafter, the activity of catalyst is evaluated by the formation rate of butynediol and the conversion of formaldehyde, which is calculated on the basis of reaction time of 300 min and catalyst mass of 0.8 g.

Exampte 13 Filterability Testing Procedure About 4 g of fresh catalyst was added to about 40 mL Dl H₂O. The stirring was started with a constant rate of 250 r/min and kept at room temperature for 24 hours, respectively. Afterwards, the slurry was filtered, and the time used for filtration was recorded to calculate the filtration rate accordingly with the unit of mL/min.

A comparison of the catalytic activity and filterability of Examples 1 to 11 and the comparative example was provided in Table 2.

Table 2 Activity and filterabi!ity comparison data

Claims

What is claimed Is:

1. A catalytic composition comprising from 20% to 80% by weight of Cu, caicuiated as CuO; from 0.5% to 15% by weight of Bi, caicuiated as Bi₂O₃; from 6.6% to 40% by weight of Ca, calculated as CaO; and from 0% to 30% by weight of Si, caicuiated as SiO₂.

2. The catalytic composition according to claim 1, wherein the catalytic composition further comprises from 0.01% to 30% by weight of Mg, calculated as MgO.

3. The catalytic composition according to claim 1 or 2, wherein the catalytic composition further comprises from 1% to 10% by weight of Bi, calculated as Bi₂O₃.

4. The catalytic composition according to any one of claims 1 to 3, wherein the catalytic composition comprises from 30% to 70% by weight of Cu, caicuiated as CuO.

5. The catalytic composition according to any one of ciaims 1 to 4, wherein the catalytic composition comprises from 6.9% to 30% by weight of Ca, caicuiated as CaO.

6. The catalytic composition according to any one of claims 1 to 5, wherein the catalytic composition comprises from 0% to 20% by weight of 8i, caicuiated as SiO₂.

7. The catalytic composition according to any one of claims 1 to 6, wherein the catalytic composition comprises from 0.1% to 25% by weight of Mg, caicuiated as MgO.

8. The catalytic composition according to any one of ciaims 1 to 7, wherein the catalytic composition comprises from 1.5% to 5% by weight of Bi, calculated as Bi₂O₃.

9. The catalytic composition according to any one of claims 1 to 8, wherein the catalytic composition has a specific BET surface area after 2hr calcination in air at 300°C, characterized by 77K nitrogen sorption, in the range of 1 to 45 m²·g^-1, preferably in the range of 1.5 to 20 m²·g^-1.

10. A process for producing a catalytic composition according to any one of claims 1 to 9 comprising: 1 ) precipitation of an acidic copper-containing aqueous solution with precipitation agent, on a particulate carrier; and

11. The process according to claim 10, wherein the calcium source is selected from the group consisting of calcium chloride, calcium hydroxide, calcium carbonate, calcium bicarbonate, calcium nitrate, caicium sulfate, calcium silicate, calcium chloride, calcium chloride, caicium formate, calcium acetate, caicium gluconate, calcium ascorbate, calcium lactate, calcium glycinate, calcium magnesium carbonate, caicium magnesium silicate, and the mixture thereof.

12. A process for using the catalytic composition according to any one of claims 1 to 9 for hydrogenation, dehydrogenation, hydrogenoiysis, or ethynyiation.