Spray-dried butynediol catalyst

Abstract

A process of forming an ethynylation catalyst includes providing an aqueous-based suspension, a copper-containing species, a bismuth-containing species, a structured species, a binder. The suspension is subjected to spray drying to form particles, and then the particles are roasted to form the ethynylation catalyst.

Description

[0001] This application is a divisional application of the Chinese invention patent application entitled “Spray-dried butynediol catalyst”, filed on August 23, 2016, with application number 201680062287.8 and international application number PCT / US2016 / 048183.

[0002] Cross-references with related applications

[0003] This application claims priority to U.S. Provisional Application No. 62 / 209,485 (filed on August 25, 2015), the entire contents of which are incorporated herein by reference. FIELD

[0005] The technology described herein generally relates to catalysts for producing butynediol. More specifically, the technology relates to methods for preparing the catalysts. background

[0007] The catalytic acetylation of methanol is also known as the "Rip reaction" or "Rip procedure". The Rip procedure uses known processes for forming copper-containing catalysts, including silicate support impregnation, co-precipitation and sediment precipitation. However, it is still difficult to prepare uniform materials. Overview

[0009] In one aspect, a method for forming an acetylation catalyst is provided. The process includes providing a water-containing slurry, the components of which include water, a copper-containing substance, a bismuth-containing substance, a structural substance, and a binder. The slurry is spray-dried to form particles, and then the particles are calcined to form an acetylation catalyst. The copper-containing substance may include but is not limited to: copper carbonate, copper oxalate, copper hydroxide, copper oxide, and cupric oxide. The structural substance may include but is not limited to: clay, mica, calcium carbonate, diatomaceous earth, aluminum oxide, carbon, and silicon. The binder includes but is not limited to: silica sol, aluminum oxide, sodium silicate, and aluminum hydrochlorate.

[0010] In any of the above statements, the particles have an average diameter of about 5 μm to about 100 μm.

[0011] In another aspect, there is provided an ethynylation catalyst formed according to the above statements.

[0012] In addition, an activation process for an acetylation catalyst is provided. The process comprises: providing an acetylation catalyst prepared by the above process, combining the acetylation catalyst with formaldehyde to form a mixture, and placing the mixture in an environment of sufficient temperature for a sufficient time to form an activated acetylation catalyst. In these processes, the sufficient temperature is 80° C. and the sufficient time is about 1 hour to about 10 hours. In any of the above statements, the activated acetylation catalyst comprises a cuprous acetylide species.

[0013] In addition, an activated ethynylation catalyst formed according to the above process is also provided.

[0014] In addition, a process for forming 1,4-butynediol is provided, which comprises contacting the activated ethynylation catalyst with acetylene in the presence of formaldehyde at a sufficient temperature and for a sufficient time to form 1,4-butynediol. Detailed description

[0016] The following provides different scenarios. It should be noted that each scenario is not an exclusive description or limitation of the scope of the content of this article. Certain content related to a certain scenario does not constitute a limitation of that scenario and can also be practiced with other scenarios.

[0017] In this document, the word "approximately" shall have the meaning that is understood by a person with ordinary comprehension of the word and shall be determined based on the context in which it is used. If a person with ordinary comprehension of the word finds the use of the word unclear, the meaning of "approximately" shall be 10% above or below the specific content in view of the context in which the word is used.

[0018] When describing elements (especially in the context described below), the use of "a", "an" and "the" and similar terms will be understood to include both the singular and the plural, unless otherwise specified or clearly contradicted by the context. The numerical ranges cited herein are only a quick way of recording and only relate to the situation where a certain individual value is within a certain range, unless otherwise specified. Each individual value is part of the specification as if it were individually cited herein. All situations described herein can be operated in the applicable order unless otherwise specified or clearly contradicted by the context. Any single and all examples or exemplary language (for example: "such as") in this document are only for better explanation of the situation and do not constitute a limitation on the statement unless otherwise specified. Any text in the specification should not be construed as an element not mentioned as an important element.

[0019] In general, a process for preparing a catalyst by spray drying is provided. After the spray drying procedure, the catalyst particles are calcined in air. The catalyst comprises copper oxide, bismuth oxide, a structural substance and a binder. The specific catalyst can be used for the acetylation of formaldehyde to form 1,4-butynediol. That is, it is an acetylation catalyst.

[0020] In one aspect, a process for preparing a specific catalyst by a spray drying method is provided. The process uses a metal-containing precursor of copper oxide or bismuth of the specific catalyst. The metal-containing precursor may include carbonates, oxalates, citrates, sulfates, nitrates and hydroxides. The precursor salt is in a suspended insoluble state in a solution, such as forming a suspension. The suspension may be milled until a desired particle size is formed in the slurry. In addition, before forming the suspension, the precursor salts may be dry milled separately, or milled together until a desired particle size is formed.

[0021] The average particle size (APS) formed may be about 0.5 μm to 10 μm. In some embodiments, the APS may be about 0.5 μm to about 5 μm, or 0.5 μm to about 3 μm, or about 1 μm to about 2 μm, or less than about 2 μm. The time for milling the precursor may be longer or shorter, depending on the desired particle size and particle size distribution. In some embodiments, it may be about 15 minutes to about 24 minutes, or about 2 hours to about 20 hours, or about 10 hours to about 20 hours.

[0022] Examples of structural material precursors include, but are not limited to, clay, talc, calcium carbonate, diatomaceous earth, aluminum, carbon, and silicon. The structural moiety plays an auxiliary role in the overall function of the catalyst. As with the precursor salts described above, the structural moiety can be milled to provide a suspension of the material, or the material can be obtained and suspended in an appropriate particle size to provide a suspension, or a pre-made suspension can be obtained.

[0023] The grinding and suspension of the precursor salt and the structural material may be carried out in a suitable solvent. For example, the solvent may be water, alcohol, nitrile, ketone or ether. In some statements where water is the solvent, the suspension formed in the corresponding statement is a water-based suspension.

[0024] After forming a suspension of the precursor salt and the structural material, a binder needs to be added to the suspension. Examples of binders may include, but are not limited to, silica sol, alumina, sodium silicate, and aluminum hydrochloride. In some statements, the binder may be SiO2. The amount of binder in the suspension is the amount of the final catalyst that needs to be bound. This amount may be from about 1wt% to about 30wt%, depending on the total solids. In some statements, the amount formed varies from about 5wt% to about 20wt%. In other statements, this value is about 10wt% depending on the total solids.

[0025] At this stage of the process, the suspension is adjusted to have an amount of solids to ensure that the material can flow and spray when spray drying is performed. For example, the solids of the suspension may be adjusted to about 1 wt % to 50 wt %, or about 1 wt % to about 25 wt %. In some cases, the solids content of the suspension may be adjusted to about 2 wt % to about 20 wt %, or about 5 wt % to about 15 wt %. In some cases, the solids content of the suspension may be adjusted to about 10 wt %. Other solutions may be added or solutions may be removed to achieve the desired solids content of the suspension.

[0026] The suspension of the precursor salt, the structural material and the binder may be spray dried using a standard wheel spray dryer or a nozzle type spray dryer. The resulting powder has an average particle diameter of about 5 μm to about 100 μm. In some cases, the average particle diameter is about 5 μm to about 60 μm, or about 10 μm to about 20 μm, or about 15 μm to about 40 μm, or about 15 μm. After the powder is obtained, it will be calcined at a temperature of about 250°C to 600°C to form a powdered calcined catalyst material. In some cases, the calcination temperature is 350°C to 500°C.

[0027] After calcination, the powdered calcined catalyst material contains about 20 wt% to about 70 wt% copper oxide and about 1 wt% to about 5 wt% bismuth oxide. The sodium content (in the form of Na2O) is usually less than 3 wt%. The powdered calcined catalyst material is mostly various types of oxides, depending on the structural material used. For example, talc contains Mg and Si, clay contains Al and Si, calcium silicate contains Ca and Si, and the binder may contain Si. Small amounts of impurities may be present.

[0028] After the catalyst is formed, it can be activated for use in the ethynylation reaction. The powdered calcined catalyst is mixed with formaldehyde in water and the pH is slightly adjusted to near base. For example, the pH may be adjusted from over 7 to 10. In some cases, the pH may be adjusted to about 8. The pH is adjusted to prevent or slow the formation of formic acid, which reacts with the copper-containing species, thereby dissolving the copper in solution rather than keeping it in suspension. The reaction of the catalyst with formaldehyde forms an activated Cu(I) ethynylation species (Cu2C2).

[0029] The activated catalyst and acetylene are then contacted with more formaldehyde in water in a pressurized reactor. The reaction with acetylene will be carried out under an inert atmosphere. Acetylene will be mixed with a gas such as nitrogen, argon or helium. The reactor is gradually heated from room temperature to about 80°C. After a certain reaction time, the acetylene absorption by the catalyst decreases and the reactor begins to cool under the acetylene flow. The reactor is flushed with nitrogen and a product containing 1,4-ethynediol and propargyl alcohol is recovered.

[0030] The above procedure provides a simplified process for the catalyst. The resulting catalyst exhibits activity comparable to or even superior to commercial catalysts for the formation of 1,4-ethynediol.

[0031] The above content provides an overview of the invention, and the following examples may provide a deeper understanding of the invention. The following examples are only examples and do not limit the invention. Example

[0033] Example 1. Copper carbonate and bismuth carbonate were mixed with water to a solid content of about 30 wt % to obtain a suspension. The suspension was then placed in a batch ball mill (ball content 60%) and rotated on a roller rack for 16 hours or until the average particle size (APS) or d 50 to 1 to 2 microns (μm). Talc or other structural materials may (if necessary) need to be subjected to the same grinding process, except that they provide an APS of 2 microns or less. The binder SiO2 (commercially known as AS40 or HS40), the overall binder content is about 10wt%. More water may need to be added to achieve a predetermined overall solid content (about 10wt% solids). The final suspension has about 10wt% solids, which is then pumped into a spray dryer, spray dried, and the final powder product is collected. Calcination is then carried out at a temperature of about 250°C to about 600°C, and more commonly at a temperature range of 350°C to 500°C.

[0034] The conditions of the spray dryer are shown in Table 1 below:

[0035] Table 1: General conditions of spray dryer:

[0036] variable set up Inlet temperature (℃) 325 Outlet temperature(℃) 110 Wheel speed (calculated, rpm) 30,000 <![CDATA[Target particle size (d 50 , μm)]]> 10-25

[0037] After calcination, the composition of the catalyst is: about 20wt% to 60wt% copper oxide, about 1.0wt% to 4.5wt% bismuth oxide, and sodium (in the form of Na2O) is usually less than 3wt%. The resulting catalyst is mostly oxides, which need to be determined according to the structural material used. For example, talc contains Mg and Si, clay contains Al and Si, calcium silicate contains Ca and Si, Contains Si. Small amounts of impurities may be present. Table 2 provides the different samples and the components that were spray dried, including their weights. Table 3 provides the data of the components used for the different samples and the formation conditions.

[0038] Table 2: Spray-dried suspension components

[0039]

[0040]

[0041] Table 3: Catalyst components and preparation conditions data

[0042]

[0043] Example 2. Catalyst testing procedure. Testing generally requires two steps. First, the catalyst is activated to form activated copper acetylide. The activated copper acetylide is then transferred to a reaction vessel.

[0044] Specifically, the catalyst activation was performed in a 4-port quartz reactor beaker containing 100 mL of formalin (37 wt% formaldehyde in water). 1.5 M NaOH was added to the formalin to adjust the pH to about 8. Formalin without water is acidic (pH = 3 to 4) due to the presence of formic acid impurities. This acidity must be neutralized before the catalyst is contacted with formalin, otherwise the copper in the catalyst may form copper formate and dissolve in the solution. Then 15 g of powdered calcined catalyst was placed in the pH-adjusted formalin. The reactor was flushed with nitrogen. Stirring was then started. Acetylene was contacted with the catalyst-formalin suspension at 50 mL / min at room temperature. The flask was then lowered and immersed in a recirculating water bath heated to 80°C. This process forms activated Cu(I) acetylated species [Cu2C2].

[0045] 1.5 M NaOH was added to the suspension to continue neutralizing the formic acid formed, keeping the pH at 8. After 5 hours, the reactor was cooled to room temperature under acetylene flow. After reaching room temperature, the acetylene in the flask was flushed with nitrogen, the reactor was opened, and the suspension was removed. It was weighed and centrifuged and then poured out, leaving a wet catalyst ready for activity testing.

[0046] Example 3. Reaction Test. For the reaction study, 45 mL of formalin was placed in a stainless steel stirred autoclave and then 0.5 g of the active catalyst (dry form) was added. As with the activity procedure, the pH of the formalin was adjusted to 8 and the reactor was flushed with nitrogen and acetylene before starting the reaction. The reactor was operated in a semi-batch manner while stirring at 1450 RPM. The pressure regulator was first set to 15 psig (reaction pressure) and acetylene was added to the reactor from a pressurized cylinder. The heater was then heated to 80°C at a rate of approximately 2°C per minute. Please note: If there is no acetylene in the reactor, it must not be heated because copper acetylide will be reduced to Cu 0, resulting in the catalyst failure. As the reaction proceeds, the amount of acetylene added is monitored by the pressure change of the pressurized cylinder. After 5 hours, the reactor is cooled in the acetylene stream and then flushed with nitrogen. The suspension is removed, centrifuged and poured off. The mixture product is analyzed by gas chromatography, and 1,4-ethynediol (main product) and propargyl alcohol (intermediate product) are quantified.

[0047] Example 4. Activity comparison. The activity of the catalysts measured as described above is provided in Table 4. The activity is compared to the commercial BASF catalyst Cu 5020P. The activity is reported as the moles of butynediol and propargyl alcohol formed per gram of CuO per minute. Note that the powdered calcined catalysts prepared by the spray drying method described above are comparable to or even better than the commercially produced catalysts.

[0048] Table 4: Activity control data

[0049] sample Formation rate of butynediol and propargyl alcohol (mol / min / g CuO) control <![CDATA[2.73 x 10- 4 ]]> 1 <![CDATA[2.63 x 10- 4 ]]> 2 <![CDATA[2.83 x 10- 4 ]]> 3 <![CDATA[2.88 x 10- 4 ]]> 4 <![CDATA[2.91 x 10- 4 ]]> 5 <![CDATA[2.81 x 10- 4 ]]> 6 <![CDATA[3.14 x 10- 4 ]]>

[0050] Although certain situations have been exemplified and described, it should be noted that those skilled in the art may vary them in a wider range of situations without departing from the art. Details are as follows.

[0051] The situations described in this article by way of example may be suitable for situations where the description is not exhaustive, one or more elements are missing, or one or more limitations exist. Therefore, words such as "include", "comprise", and "contain" should be understood in a broad and non-restrictive manner. In addition, the terms and expressions used in this article are intended to be used as descriptive terms without limitation. Therefore, such terms shall not be used to express equivalent features that do not include the features shown or described. However, it is recognized that different modifications may be made within the scope of the stated technology. In addition, the term "mainly comprising" can be understood to include the specific elements described, and may also include other elements that do not significantly affect the basic and important features of the described technology. Any element not specifically stated is not included in the word "comprising".

[0052] The content disclosed in this article is not limited to the specific circumstances described in this application. If people familiar with the industry deem it necessary, they can be modified and changed without departing from its spirit and scope. For those familiar with the above-mentioned content, within the scope disclosed in this article, in addition to the circumstances described in this article, it is obvious that there will be other methods with equivalent functions. Such modifications and changes need to be within the scope described in the appendix. The disclosure made in this article is limited to the contents described in the appendix and the full scope of the contents equivalent to the contents described. It should be noted that the content disclosed in this article is not limited to certain specific processes, reagents, compound compositions or biological systems, and these aspects will obviously change. It should also be noted that the terms used in this article are limited to describing specific circumstances and have no restrictive meaning.

[0053] In addition, for features or circumstances described herein as falling within the Markush category, persons familiar with the industry will recognize that such disclosures may also be described using any member or sub-category of the Markush category.

[0054] Those familiar with the industry will understand that all ranges provided herein include possible subranges and combinations of subranges, regardless of the purpose, especially when providing a written description. Any range described is described in an adequate manner and can be divided into two, three, four, five, ten, etc. Each range has no limiting meaning, so each range discussed herein can be taken as the lower third, the middle third, and the upper third. Those familiar with the industry should also understand that all words similar to "at most", "at least", "greater than", "less than" and similar words, including the quoted numbers, refer to ranges that can be divided into the subranges described above. Finally, as those familiar with the industry know, the range includes each independent component unit.

[0055] All publications, patent applications, patents and other documents cited in this document are hereby incorporated by reference, and each specifically referenced publication, patent application, patent or other document is attached to this document in its entirety. Definitions contained in the text of the incorporated reference documents shall not be included if there is a conflict with the definitions in this document.

[0056] Additional statements are described below.

Claims

1. A method for forming an ethynylation catalyst, the method comprising: providing a water-based slurry comprising water, a copper-containing substance, a bismuth-containing substance, a structural substance, and a binder; spray drying the slurry to form granules; and The particles are calcined to form the ethynylation catalyst.

2. The method of claim 1, wherein the copper-containing substance comprises copper carbonate, copper oxalate, copper hydroxide, copper oxide or cuprous oxide; and / or the bismuth-containing substance comprises bismuth carbonate, bismuth oxalate, bismuth hydroxide, bismuth oxide and bismuth acetate; and / or the structural substance comprises clay, talc, calcium silicate, diatomaceous earth, alumina, carbon or silicon dioxide; and / or the binder comprises silica sol, alumina sol, sodium silicate or aluminum chlorohydrate.

3. The method of claim 1, wherein the particles have an average particle diameter of about 5 μm to 100 μm; or the particles have an average particle diameter of about 5 μm to about 60 μm; or the particles have an average particle diameter of about 15 μm.

4. An ethynylation catalyst obtained by the process of claim 1.

5. A method for activating an ethynylation catalyst, the method comprising: Providing the ethynylation catalyst of claim 4; exposing the ethynylation catalyst to form a mixture, and The mixture is maintained at a sufficient temperature and for a sufficient time to form an activated ethynylation catalyst.

6. The method of claim 5, wherein the sufficient temperature is about 80°C; and / or the sufficient time is about 1 hour to about 10 hours.

7. The process of claim 5, wherein the activated ethynylation catalyst comprises copper acetylide.

8. An activated ethynylation catalyst formed by the process of claim 5.

9. A method for forming 1,4-butynediol, the method comprising: The activated ethynylation catalyst of claim 8 is exposed to acetylene in the presence of formaldehyde at a sufficient temperature and for a sufficient time to form 1,4-butynediol.

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