CN-122006750-A - Catalyst, process for its preparation and process for selective hydrogenation

Abstract

The invention relates to a method for producing 1, 4-butanediol. The method may comprise reacting a solution comprising 1, 4-butynediol with hydrogen in the presence of an effective amount of a catalyst. The catalyst may comprise copper.

Inventors

• S. SCHMIDT

Assignees

• 格雷斯公司

Dates

Publication Date

20260512

Application Date

20210324

Priority Date

20200330

Claims (6)

1. 1. A method of preparing a catalyst, the method comprising: melting and mixing copper, a first metal and a second metal to form an alloy precursor, Wherein the first metal is selected from the group consisting of Ni, co, fe and mixtures thereof and the second metal is selected from the group consisting of aluminum, molybdenum, chromium, iron, tin, zirconium, zinc, titanium, vanadium and mixtures thereof.
2. 2. The method of claim 1, wherein the first metal is Ni and the second metal is aluminum.
3. 3. The method of claim 2, wherein Ni is present in an amount ranging from about 30 wt% to about 60 wt% of the alloy precursor, aluminum is present in an amount ranging from about 40 wt% to about 65 wt% of the alloy precursor, and copper is present in an amount ranging from about 1.0 wt% to about 12.0 wt% of the alloy precursor.
4. 4. The method of claim 2, wherein Ni is present in an amount ranging from about 40 wt% to about 49 wt% of the alloy precursor, aluminum is present in an amount ranging from about 50 wt% to about 60 wt% of the alloy precursor, and copper is present in an amount ranging from about 1.0 wt% to about 10.0 wt% of the alloy precursor.
5. 5. A method according to claim 3, further comprising: contacting the alloy precursor with an aqueous base to produce the catalyst, Wherein the catalyst comprises copper in an amount in the range of about 1.0 wt% to 12.0 wt% of the catalyst.
6. 6. A process according to claim 3, wherein the catalyst is a skeletal metal catalyst.

Description

Catalyst, process for its preparation and process for selective hydrogenation The application is a divisional application of the application application with the application number of '202180038880. X', and the application name of 'catalyst, preparation method and selective hydrogenation method'. Technical Field The present invention relates to a catalyst, and more particularly, to a catalyst for preparing 1, 4-butanediol, a preparation method thereof, a selective hydrogenation method employing the catalyst, and an alloy precursor for preparing the catalyst. Background Skeletal metal nickel catalysts in the form of a particulate fixed bed are commonly used industrially to prepare Butanediol (BDO), a component in the preparation of polyesters, from the unsaturated compound 1, 4-Butynediol (BYD). One form of skeletal metal nickel catalyst is made by the Raney process, starting from an alloy containing at least two metals, such as nickel and aluminum. Optionally, other metals or compounds are added in minor amounts as "promoters" to enhance the activity, selectivity or durability of the catalyst. US 6,262,317 discloses a process for the preparation of 1, 4-butanediol by continuous catalytic hydrogenation of 1, 4-butynediol. The process comprises reacting 1, 4-butynediol with hydrogen in the presence of a heterogeneous hydrogenation catalyst in a liquid continuous phase. The catalyst typically comprises one or more elements of transition groups I, VI, VII and VIII of the periodic table of elements. The catalyst preferably further comprises at least one element selected from the elements of main groups II, III, IV and VI of the periodic table, elements of transition groups II, III, IV and V, and lanthanides as promoters to increase activity. The promoter content of the catalyst is generally up to 5% by weight. The catalyst may be a precipitated, supported or framework type catalyst. CN 201210212109.2 discloses a method for preparing and activating a skeletal metal nickel-aluminum-X catalyst, which is specifically used for preparing 1, 4-butanediol by hydrogenating 1, 4-butynediol. X represents Mg, B, sr, cr, S, ti, la, sn, W, mo or Fe. U.S. patent application Ser. No. 62/715,926 discloses a process for preparing 1, 4-butanediol. The method comprises reacting a solution comprising 1, 4-butynediol with hydrogen in the presence of a catalyst comprising cerium as a promoter. The process can significantly reduce the formation of butanol by-product. Current catalysts typically have a predictable finite life. Current processes produce n-butanol, acetals (e.g., 2- (4-hydroxybutoxy) tetrahydrofuran) and other byproducts at progressively increasing rates until a maximum specification limit is reached, which defines the end of the useful life of the catalyst of the bed. Acidic Al species present in skeletal metal catalysts, such as hydrated alumina residues from leaching processes, are believed to be one of the primary reasons for the production of by-products comprising butanol and acetals. Skeletal metal catalysts may generally contain small additions of elements as promoters whose functions include improving the activity, selectivity and stability of the catalyst in the chemical environment of a given hydrogenation process. Some promoters for framework metals (such as conventional Mo, cr, or Fe) may actually increase the formation of butanol by-product due to the increased surface acidity. Operating conditions such as relatively low temperature, relatively high pressure and feed pH control have been previously optimized and their combination still does not adequately inhibit butanol and acetal formation. Butanediol is the major component in the preparation of polyesters. Since downstream use has impurity limitations on butanediol, reducing contaminants in butanediol during the process of making butanediol can significantly reduce costs, such as those associated with subsequent separation (e.g., distillation) of impurities and butanediol. Disclosure of Invention The present invention provides a process for preparing 1, 4-butanediol from a1, 4-butynediol solution in the presence of a catalyst comprising copper. In addition to maintaining the desired low level of n-butanol, another key by-product in the final 1, 4-butanediol product, the process significantly and unexpectedly reduces the amount of the major by-product acetal (2- (4-hydroxybutoxy) tetrahydrofuran). Thus, one example of the present invention is a process for preparing 1, 4-butanediol. The method may include reacting a solution comprising 1, 4-butynediol with hydrogen in the presence of a catalyst comprising copper as a promoter. Another example of the invention is an alloy precursor for a catalyst for the preparation of 1, 4-butanediol. The alloy precursor may comprise the first metal, the second metal, and copper in a range of about 1 wt% to about 10 wt% of the alloy precursor. Another example of the present invention is a catalyst for the preparation of 1,