JPS5931720A - Manufacture of 1,4-butinediol - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for coprecipitating malachite with bismuth, a process for producing copper acetylide complexes as ethynylation catalysts starting from such coprecipitation, and the complexes produced.

It is known that in the formation of 1,4-butynediol by the reaction of acetylene with formaldehyde in the presence of a copper acetylide complex catalyst, it is desirable to prevent the formation of cuprene, or polymerized acetylene, by the use of an inhibitor such as bismuth oxide. It is being U.S. Patent No. 2,30
No. 0,969, Retsubara (1942) discusses the use of several such inhibitors when producing and using such catalysts at elevated pressures, such as about 20 atmospheres. U.S. Patent No. 3,650,9
No. 85 describes the utility of bismuth oxide as a cuprene inhibitor in the production and use of copper acetylide catalysts at low partial pressures of acetylene (less than 2 atmospheres). None of these prior art patents shows anything about how the bismuth component is uniformly contained in the catalyst itself.

In the preparation of low-pressure catalysts according to U.S. Pat. No. 5,650,985, if bismuth oxide carbonate is added separately to the preformed malachite, it is unsatisfactory because it separates in the final formed catalyst. found to yield results. It would therefore be desirable to have a satisfactory method of co-precipitating bismuth in the catalyst precursor, basic copper carbonate or malachite.

Basic copper carbonate 0u2 (O
H)2005 is commonly produced by one of two precipitation methods. The first method is to neutralize a solution of a copper salt, such as copper nitrate or copper chloride, with sodium or potassium carbonate or bicarbonate to a pH of ZO. Initially, copper carbonate, or amorphous OuO03.IC(H2O), precipitates in the form of a viscous gelatinous substance, which upon heating desorbs CO2 and is gradually converted to malachite. Malachite crystal precipitates prepared by this technique generally consist of irregularly shaped particles with average particle cross-sectional dimensions ranging from less than 1 micron (μ) to more than 25 μ.

If the gel had been sufficiently assimilated (set), the irregularity of crystallite size and its wide distribution during crystallization would be the result of its destruction as the gel precipitated.

Irregularly shaped crystallites and particle size range 1/-1
The distribution is rather undesirable for use as a precursor in the production of cuprous acetylide, an ethynylation catalyst.

Another method of precipitating malachite is to add the copper solution described above and the carbonate neutralizer described above simultaneously with stirring so as to maintain the pH in the range of 5 to 8. The irrigated carbonate steel thus obtained also converts to malachite at ambient temperature, but more rapidly as the temperature increases.

This procedure produces a more regular crystalline product consisting of agglomerates of individual crystallites with cross-sectional dimensions averaging about 2-6 microns. These agglomerates range in size up to 30μ. As with the first method of adding the carbonate neutralizers to the copper solution, this method of adding them simultaneously also initially forms amorphous hydrated copper carbonate.

It would be desirable to have a process for producing bismuth-loaded basic copper carbonate crystalline particles that are uniform and of relatively large particle size. Uniform dispersion of bismuth within the particles is desirable for forming the ethynylation catalyst, in which case the bismuth component remains therein) and remains effective in inhibiting cuprene formation.

In certain embodiments, the present invention provides a method for producing crystalline particles of basic carbonate steel having bismuth uniformly dispersed in an amount ranging from 1 to 5% by weight based on the amount of copper present. It is something to do.

The method consists of three steps. The water-depleted copper carbonate particles are precipitated by first adding a solution of the cupric salt and a solution of the alkali metal carbonate or bicarbonate to water to form a reaction mixture. Those solutions have a pH of about 5.0~a
The ratio is such that it is kept within the range of 0. The hydrated carbon e@ is then converted to basic carbonate steel in the reaction mixture at a temperature of at least about 60°C. This transformation occurs through the formation of malachite crystallite nuclei from amorphous hydrated copper carbonate. When steel, bismuth and carbonate are added, more malachite precipitates out on these transformed nuclei. Nucleated crystalline particles and agglomerates of such particles grow with bismuth uniformly incorporated into the particles. The reaction mixture is maintained at a temperature of at least about 60° C. during growth. cupric salt, bismuth salt and sodium carbonate or bicarbonate in proportions to maintain the pH in the range of about 5.0 to aO until the average cross-sectional size of the crystallite agglomerate is at least about 10 microns. Add each solution of sodium.

Bismuth content is herein expressed in weight percentages based on the amount of copper present. Parts, fractions, and proportions herein are by weight unless otherwise indicated.

Although it is necessary to have bismuth present during grain growth, it is desirable, and often in practice necessary, to also have it present during the precipitation and nucleation stages.

Co-precipitated basic copper-bismuth carbonate particles can be used to prepare cuprous acetylide complexes useful as ethynylation catalysts.

The particles of basic copper-bismuth carbonate are treated as a slurry in an aqueous medium at 50 DEG to 120 DEG C. with formaldehyde and acetylene at a partial pressure not greater than 2 atmospheres. The aqueous medium has a pH of 3 to 10 at the start of action. Preferably, the reaction is continued until all of the copper precursor has been converted to cuprous acetylide complex.

It is desirable that the medium in which this action takes place has a pH in the range of 5 to 8, at least initially.

The produced catalyst essentially has the general formula % (wherein W34.xxO, 24~4.0.7m1
124 to 2.40 and z = CJ, 67 to 2.80 and bismuth is present in 1 to 5 degrees). is a cuprous acetylide complex. The complex particles have a total surface area of at least 5 m2 and an average particle cross-sectional size of at least 10 microns.

Preferably the particulate complexes have a total area of 15 to 75 ff12/p, with average particle cross-sectional dimensions ranging from 10 to 40 microns, 20 to 66 inches of steel, 2 to 12.5 copper atoms.
0,2 to 2 hydrogen atoms per carbon atom, 6 o, i to 1 oxygen atoms and 2 to 2 hydrogen atoms per carbon atom
Contains 41 bismuth.

Compared to the conventional basic carbonate steel crystal growth method, the method of the present invention has a rapid precipitation of water efficiency i″L, fc copper carbonate, subsequent nucleation and hydrated carbonate. The conversion of copper to basic copper carbonate (malachite) is utilized, the nucleation and conversion of which is facilitated by elevated salinity, eg, above 60°C.

A major portion (such as at least the copper) of the reaction components to produce basic copper carbonate is not added to the reaction mixture until after conversion to basic copper carbonate. At this point, the copper salt, neutralizing agent, and bismuth readily combine to produce a uniform dispersion of bismuth into the basic copper carbonate crystalline particles of uniform and large particle size. This crystal growth prevents the initial formation of gelatinous hydrated carbonate steel.

If the complete production of basic copper carbonate crystals, including precipitation formation, nucleation and growth, is carried out at elevated temperatures, e.g. above 60°C, hydrated copper carbonate may exist for a long time. There isn't. Nucleation and transformation occur rapidly] and initial nuclear growth is the main phenomenon occurring. Operating all stages of production at elevated temperatures therefore leads to the formation of fewer and larger particles. In practice, each step will occur at lower temperatures, such as room temperature (about 23°C). Before the growth of the crystals reduces the amount of reactants, a large number of nuclei are formed and converted to malachite, resulting in an increase in particles of smaller size.

Also, in the process of producing malachite at lower temperatures, the bismuth component is not uniformly contained in the basic copper carbonate produced in this process, but is used as an ethynylation catalyst during or after the formation of the carbonate. The cuprous acetylide complex tends to separate during either use of its carbonate to produce the cuprous acetylide complex. It is therefore advantageous to use the process of the present invention to produce a basic copper carbonate-bismuth co-precipitate to be used in preparing ethynylation catalysts.

To produce crystallites and agglomerates of much smaller size, nucleation is carried out at lower temperatures followed by increasing the temperature above 60°C, resulting in relatively rapid conversion and growth and uniform dispersion of the bismuth. can be done. In order to produce large size crystallites and agglomerates,
Nucleation also takes place at much higher temperatures, for example above 60°.

Greater uniformity in particle size can be provided if the pH increases by at least 1.0 units between the nucleation and growth stages.

Crystal growth occurs most frequently in the supersaturation zone of the solubility-temperature curve. The supersaturation band is very high p
There is a wide range in g values for these products. Therefore, a higher pH within a limited range will lead to further deposition on the existing nuclei, and if the reaction continues to be carried out in the supersaturation zone, it will lessen the formation of new undesirables. Probably.

The conversion of hydrated carbonate steel to malachite can be easily observed as malachite nucleates. Hydrated copper carbonate is blue in color and is easily formed into a structureless gelatinous mixture.

Malachite is green and crystalline.

When sodium carbonate is added to a pH 3 copper nitrate solution, the reaction product forms as a thick gel as the pH increases to 4. Malachi's K changes while the subsequent rising and stirring of the gel breaks down the gel, producing highly irregular particles that are related to the size of the broken gel.

p) (above about 80 and at elevated temperatures, the carbonic acid-like hydrate of the 13-isomorphic form begins to transform into undesirable copper oxides. At pH below 5.0, gel formation is hindered.

Sodium iodide can be added separately during catalyst formation. This produces some bismuth oxyiodite in the catalyst, which acts as another inhibitor to cuprene formation.

Preferably, the catalyst has an agglomerate size of about 15-20 microns. Larger particles are advantageous over smaller particles because they are filtered and dried more quickly, and dusting and banding does not occur during settling. The agglomerate size of 50 microns is too large to be desirable since the activity of the catalyst is reduced. Catalyst particles that are too small make filtration difficult. The size of the agglomerates can be easily controlled by adjusting the temperature and pH during the basic carbonate steel manufacturing step.

14- During the ethynylation reaction, acetylene prevents the i-side conversion of cuprous to elemental steel or cupric in the catalyst. This is desirable because elemental copper is the catalyst for polymerizing acetylene to cuberene. Cuprene is highly undesirable in these reactions because it tends to clog the filter and cannot be easily removed.

Under certain conditions in manufacturing operations, the flow of acetylene to the reactor is shut off due to an emergency or sudden loss of supply. Bismuth, which is uniformly contained in the catalyst in the form of oxidized carbonates, helps protect the catalyst from such decomposition at heat and even in the absence of acetylene.

Above 4 or 5 parts of bismuth, the second phase tends to separate from the catalyst after several weeks of operation in the ethynylation catalyst. This is evidenced in the production of particulates which themselves make filtration difficult.

Such separation also tends to deactivate the bismuth in the catalyst.

At solubility levels of about α5 ppm in the ethynylation reaction medium, bismuth is leached out of the catalyst.

This is a problem when the bismuth content of the catalyst is greater than about 30 mm, but is not a serious problem until the bismuth content is about 500 mm or greater.

In a preferred method according to the invention, bismuth nitrate is dissolved in a steel nitrate solution at the desired concentration.

It is then simultaneously added to the crystallization tank along with the sodium carbonate. While the crystals are growing, the pH is kept between 6 and 7.
and the temperature is in the range of 60 to 80°C. To obtain large crystals, the temperature is also in the range for precipitation and nucleation from the beginning. Bismuth is effectively coprecipitated and uniformly distributed in the resulting malachite. When such bismuth-containing malachite is utilized to produce cuprous acetylide complexes, which are ethynylation catalysts for butyne diol synthesis, substantial improvements are made in the filtration capacity and stability of the catalyst. Ru.

Bismuth-containing malachite was initially nucleated according to the present invention using 9 techniques, and 1 g 6.2 qI 6.3 chi,
Bismuth concentrations of 4T, 8%, 10q6, and 15T were produced. The resulting malachite is then used to produce an ethynylation catalyst. The catalyst thus obtained is then subjected to long-term life testing to determine its improved stability and performance as indicated by the absence of cublene formation. For comparative purposes, a catalyst is similarly prepared using commercially available malachite. The life test is conducted for a period of 17 to about 100 hours or more, at which point the catalyst is removed and tested for the presence of cuberene. Coubray is easily detected due to its copper color, and it is commonly suspended on the surface of the formaldehyde-water solution used to make butyne diol. Excess bismuth salt can also be eluted from the catalyst and form other colored residues.

Life test results show that catalysts made from bismuth-free malachite precursors produce substantial amounts of cuprene during a 100 hour life test. Analogous to the sudden disappearance of acetylene in a butynediol production operation, if the catalyst is kept hot in the absence of acetylene, even more cuprene is produced.

If an additional 50% of bismuth is mixed with bismuth-free malachite in the form of bismuth subcarbonate, and the mixture is then converted into a catalyst, substantial polyprene formation is still evident when the catalyst is evaluated.

Traces of quazolene are also observed with catalysts containing one gram of bismuth, whereas catalysts made from malachite co-precipitated with larger amounts of bismuth remain free of cuprene. Catalysts produced with bismuth or more co-precipitated in malachite can be exposed to an acetylene-free environment without deterioration causing excessive cuprene formation, which is considered to have reached the end of the useful life of the catalyst. It can be maintained at an elevated temperature, for example 70 to 95° C., for a short period of time (for example up to about an hour).

Bismuth additions of 5 and more result in some amount of bismuth separating from the catalyst after extended use. Bismuth concentrations above 3 or 4 degrees therefore appear to be less desirable, and concentrations in the range of 2-4'% appear to be optimal for overall operation. One preferred catalyst with a bismuth content of 3% was used for 20 days in the production of butyne diol without any evidence of degradation or cuprene formation. Further, the catalyst having a relatively large and uniform particle size obtained by the present invention can be more easily treated.

In butynediol production processes where the catalyst system operates as a slurry and the product is removed by a candle filter, larger particle sizes can increase the filtration rate.

Example 1 Malachite-44Bi (cold start) A crystalline particulate synthetic malachite containing 4 tibismuth is produced according to the present invention as follows.

Two liquid streams are added simultaneously to a reaction vessel containing 300 cc of water. -The liquid flow is a saturated aqueous solution of Na2003, and the other is 0u(NO5)2 ・3H20'+ OD
9sBi (No3) 3・5E (202,52jL,)
(It is an aqueous solution containing No. 31 [1ee and 90% H2O.) When these liquid streams are added at a rate that continuously maintains the pH in the precipitation container at about 6.5, and heat is gradually added from the beginning, precipitation occurs. The following table shows the solution addition rate, measured for the nitric acid steel solution still to be added,
The time from the start of the addition and the temperature of the reaction mixture are indicated.

Table ■ 0 35 150 10 (nucleation) 70 1257
2 22! 15 75 -0-2l- The reaction product is aged in water to reach a pH of 8.0, then washed and dried. The particles have an average cross-sectional size of 15-20 microns. The product contains 40% bismuth homogeneously dispersed in crystalline particles.

about 14 to 1 of their reactants until nucleation and transformation (although they may occur simultaneously) occur.
It is desirable to grow bismuth-containing malachite crystals by adding only /6 and then adding the remaining reaction components after nucleation.

Example 2 Malachite - Crystalline particulate synthetic malachite containing 6Bi (cold start) 3 dibismuth is prepared according to Example 1 with the exception that Bi(NO3)3.
5H201,749 is used. The following table shows data similar to that of Example 1 and also gives several times during the reaction the notation I) H 22-.

Table ■ [] 85 140 6.5 15 75 125 6.5C nucleation)
35 75 50 7.441 7
5 25 7.450 75 -
0-6.7 Nucleation is achieved at pH 6.5, then the pH is raised to 7.5 to grow crystals. Crystallization is terminated at pH 6.8 to render all malachite insoluble. The product is then aged in pHaO, washed, filtered and dried. The resulting product has particles having a cross-sectional dimension of 15 to 25 microns and containing well-dispersed bismuth at the 3-inch level.

Example 3 Preparation of Catalyst In the preparation of a typical catalyst, a glass reaction with a jacket heater is carried out in which the bismuth-containing Malachi 45p and 0u25jl are combined with 67 polyformaldehyde 6002 and 0aO032p to neutralize the formic acid formed. Put it in a bowl. A stream of 02H2 diluted with N2 is passed into the vessel using a sintered glass frit to distribute the gas. The temperature is controlled between 70 and 80°C and the pressure is controlled at 4-5 psig. As the malachite is converted to copper acetylide, CO2 is desorbed, so the system is equipped with an exhaust port to remove CO2. The system is also equipped with a small gas recirculation pump to recirculate unreacted 02H2, and additional 02H2 and N2 are added to maintain pressure. The 02H2 concentration in the exhaust gas, as measured by gas chromatography, is generally kept in the range of 2 to 5 volumes to obtain the most active catalyst. all CO2
After removal, the reactor is cooled, the contents removed and the catalyst washed with water to remove the product butynediol and unreacted formaldehyde. The catalyst thus obtained is stored in water until evaluated for stability and long-term activity.

Example 4 Evaluation of Catalyst (Lifetime Test) For evaluation, a catalyst derived from malachite stock 459 is placed in a jacketed container containing 600 cc of 15-thiformaldehyde solution. Acetylene gas is passed through a sintered glass frit to achieve the necessary distribution and mass transfer.

25- Increase the reactor temperature to 90°C and after 8 hours to 95°C. Acetylene is continuously supplied at the same time as the 37q6 formaldehyde solution is supplied so as to maintain the formaldehyde concentration at a steady state of 10%. The catalyst remains in the reactor as the product is continuously recovered through a sintered glass filter. The pH in the reactor was measured by a pH test at -fC of 6. A solution of sodium bicarbonate is added continuously to maintain Ω~6.2.

The total pressure of the reactor is maintained at 5pθ1 g. The activity is measured as (weight units of O 2 H2 consumed)/time/(weight units of copper in the reactor) and is calculated continuously from the rate of consumption of formaldehyde.

The life test is conducted for approximately 100 hours or more, after which the system is cooled, the catalyst is recovered, filtered and washed to remove reaction components and products, and the cuprene content is tested for 26-hours. do. Cuprene is easily detected (by its characteristic copper color) and tends to float on the surface of the aqueous layer, beneath which the fF-rated catalyst is stored.

Table 2 below summarizes the results of a life test conducted using the cuprous acetylide catalyst of the present invention. If more than 5 inches of bismuth is used, a variety of colored substances will be deposited on the catalyst. Bismuth salts separate as a result of leaching of bismuth from the catalyst. Cuprene is not detected when bismuth is 1 or more. However, cases in which bismuth is not co-precipitated with 72 kites (tests 11 and 12) are excluded.

Catalysts containing 2H, 5% and 15H bismuth are
Even after exposure to elevated temperatures in the absence of acetylene, no subsequent formation of harmful prenes is observed.

Table ■ 1 15 210 0.75
B1 Imperial Encouragement 2 15 175 0.63
None B1 salt or separation 310 207 0.6
None B1 salt or separation 4 8 85
0.7 None B1 salt separated 5518
7 α7～α6 None 6 3205
[No 17 Transparent 7 2
None 8 1 105 15 Small amount 9 1 102 0.65 Small amount 10 0 90 α5
Malachite that does not contain a small amount of B1 The novel technical matters demonstrated by R) according to the present invention will be summarized below.

t the following steps: adding a solution of a cupric salt and a solution of an alkali metal carbonate or bicarbonate to water in proportions to maintain the pH in the range of about 5.0 to aO to form a reaction mixture; precipitating particles of hydrated carbonated steel by nucleating and converting the hydrated copper carbonate to basic carbonated steel at a temperature of at least about 60° C. in the reaction mixture; By adding a solution of a cupric salt, a bismuth salt, and an alkali metal carbonate or bicarbonate at a temperature of at least about 60° C. in proportions such as to maintain the pH of the reaction mixture in the range of about 5.0 to aO. 29-- consisting of precipitating basic copper carbonate containing rubismu and growing a conglomerate of nucleated crystalline particles until the average cross-sectional size of the crystallite conglomerate is at least about 10 microns. A method for producing an agglomerate of basic copper carbonate crystalline particles in which bismuth is uniformly dispersed in an amount ranging from 1 to 5 by weight based on the fiK of copper.

2. The method according to item 1 above, wherein the alkali metal is sodium.

6. The method according to item 2 above, wherein the cupric salt is copper nitrate and the bismuth salt is bismuth nitrate.

4. The pH of the growth stage is at least 1 greater than the pH of the precipitation stage.
．． 0. The method according to item 1 above. 5. The method of item 2 above, wherein the temperature during the growth step is in the range of about 60-70°C.

& The method according to item 2 above, wherein the pH during the growth stage is in the range of 6.0 to 7.0.

1. The method of item 5 above, wherein the pH of the growth stage is about 6.5.

30-a The method of claim 1, wherein the bismuth content of the agglomerate ranges from 2 to 4% by weight, based on the amount of copper present.

9. The method of claim 1, wherein at least about two-sixths of the copper is added to the reaction mixture during the growth stage.

1 [L essentially general formula % formula %) (However, in the formula, in the case of W-4 x-0.24 to 4.0.7
=[L24~2.40 and z-0,67~2.80, and bismuth is 1~2.80 based on the amount of copper present.
copper, carbon, in proportions corresponding to (present in an amount of 5% by weight)
A particulate cuprous acetylide complex comprising hydrogen, oxygen and bismuth, the complex particles having a total surface area of at least 5 m2/P and an average particle cross-sectional size of at least 10 microns.

11. have a total surface area of 15 to 75 m2/l, and have an average particle cross-sectional size in the range of 10 to 40 μ; and 20 to 6
6 by weight of copper, 2 to 12.5 carbon atoms per atom of copper, per atom of carbon. 90. 2 to 2 hydrogen atoms, 1 to 1 oxygen atom per carbon atom, and 2 to 4% bismuth by weight based on the amount of copper present. Particulate cuprous acetylide complex.

12. In the following steps, the solution of the cupric salt and the solution of the alkali metal carbonate or bicarbonate are brought to a pH of about 5.0 La.

(by adding the hydrated copper carbonate particles to water to form a reaction mixture in such proportions as to maintain the hydrated copper carbonate particles in the reaction mixture at a temperature of at least about 60°C, and Convert the hydrated copper carbonate to basic copper carbonate and add cupric salts, bismuth salts and alkali metal carbonates to the reaction mixture until the average cross-sectional size of the crystallite agglomerates is at least about 10 microns. or each solution of bicarbonate,
a collection of nucleated crystalline particles by precipitating a basic steel carbonate containing bismuth at a temperature of at least about 60° C. in proportions to maintain the pH of the reaction mixture in the range of about 560 to aO. The agglomerated basic copper carbonate is grown as a slurry in an aqueous medium (which has a pH of 3 to 10 at the start of the process) and is then treated with formaldehyde at 50 to 120°C. and acetylene at a partial pressure not greater than 2 atmospheres and continuing the reaction until a complex according to paragraph 10 is obtained, based on the amount of copper present. A method for producing a particulate copper acetylide complex in which bismuth is uniformly dispersed in an amount of 50%.

13゜The above aqueous medium has a pH at the start of the above action.
13. The method according to item 12, wherein the method is 5 to 8.

146. The method of claim 12, wherein said agglomerated basic carbonate steel has a total surface area of at least 5 m2/9.

15. The method of claim 12, wherein the temperature, formaldehyde concentration and acetylene pressure are maintained until substantially all of the copper precursor is converted to copper acetylide complex.

Patent Applicant E.I.P. de Nemours-7nd Life Company 34-

Claims (1)

[Claims] Essentially the general formula %) (wherein, when w = 4, X = 0.24 to 4.
0, y = 0.24-2.40 and rs = 0.
67 to 2.8 Cl, and bismuth is present in an amount of 1 to 5% by weight based on the amount of copper present); reacting acetylene and formaldehyde in the presence of a particulate cuprous acetylide complex, the complex particles having a total surface area of at least 5 m2/y and an average particle cross-sectional dimension of at least 10 microns, A method for producing 1,4-butynediol.