JP2638614B2 - Method for producing molybdenum / alkylene glycol complex useful as epoxidation catalyst - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molybdenum compound, and more particularly, to an improved method for producing a molybdenum alcohol complex useful as an olefin epoxidation catalyst.

Other related methods in the art Epoxidation of olefins to obtain various epoxide compounds has been studied for a long time by those skilled in the art. It is well known that the reactivity of various olefins depends on the number of substituents on the carbon atom having a double bond. Ethylene itself has a relatively lowest epoxidation rate, with propylene and other alpha-olefins being the second lowest. Compounds of the formula: R ₂ C = CR ₂ , where R simply represents an alkyl or other substituent, can be epoxidized very quickly. Thus, as the number of substituents on the double bond carbon increases, it becomes easier to epoxidize the bond.

The production of ethylene oxide from ethylene has long been
It has been carried out by reaction with molecular oxygen over a silver catalyst. Numerous patents have been granted for various silver contact processes for ethylene oxide production. Unfortunately,
Silver catalysis has not been commercialized for olefins other than ethylene. For a long period of time, commercial production of propylene oxide could only be done via a cumbersome chlorohydrin process.

Another commercial method for producing substituted oxides from α-olefins such as propylene is described by John Kollar, 196
It was not discovered until the work of the 0's. In his U.S. Pat.No. 3,351,635, an olefinically unsaturated compound is reacted with an organic hydroperoxide in the presence of a molybdenum, tungsten, titanium, columbium, tantalum, rhenium, selenium, chromium, zirconium, tellurium or uranium catalyst. It is taught that organic oxide compounds can be produced thereby. U.S. Pat. No. 3,350,422 to Kollar teaches a similar method using a soluble vanadium catalyst.

However, while Kollar's work has been identified as of great importance in the development of commercial propylene oxide processes that do not rely on the chlorohydrin process, the Kollar catalytic process (molybdenum is the preferred catalyst) has been It has been found to have problems. For example, a large amount of alcohol is produced corresponding to the peroxide used. The use of t-butyl hydroperoxide as a coreactant produces substantially equimolar amounts of olefin epoxide and t-butyl alcohol. Another problem is that olefin oligomers are formed as by-products. When propylene is an olefin to be epoxidized, various propylene dimers, and in some cases, so-called hexenes, are usually formed. In addition to being undesirable in that this is not the desired use of propylene, problems arise in separating the desired propylene oxide from the product mixture. In addition, molybdenum catalysts are not stable or have low catalyst recovery for recycle use.

Various methods have been investigated in an attempt to improve the molybdenum-catalyzed epoxidation of propylene. One approach attempts to improve the catalyst itself. Patents covering the manufacture of various molybdenum epoxidation catalysts include U.S. Patent No. 3,362,972 to Kollar. A molybdenum compound in which molybdenum has a valence of +6 or a vanadium compound in which vanadium has a valence of +5 is heated together with a carboxylic acid having 4 to 50 carbon atoms having at least 4 carbon atoms per carboxyl group. By doing so, a hydrocarbon-soluble salt of molybdenum or vanadium can be produced. Beck
U.S. Pat. No. 3,578,690 issued to er discloses that a molybdate can be prepared by directly reacting a carboxylic acid with a molybdenum compound while removing the water formed.

It is possible to produce an olefin epoxidation catalyst by reacting molybdenum trioxide with a monovalent saturated alcohol having 4 to 22 carbon atoms, or a mono- or polyalkylene glycol monoalkyl ether or a mixture thereof. U.S. Patent No. 3,48, issued to Bonetti et al.
No. 0,563. These catalysts contain only 0.07 to 0.93% molybdenum, and the molybdenum content is too low for commercial use and is undesirable.
Bonetti et al. Did not realize that the ratio of alcohol to molybdenum compound reactant was important to maximize molybdenum content and to provide a soluble, active epoxidation catalyst. They also do not show any of the advantages of adding ammonium hydroxide to the preparation or the significant factor found when reacting molybdenum trioxide with 2-ethyl-1-hexanol.

In U.S. Patent No. 4,434,975 to ARCO,
It, molybdenum catalyst by saturated alcohols or glycols having 1 to 4 carbon atoms, such as ethylene glycol or propylene glycol, metallic molybdenum and organic hydroperoxide is reacted with peroxide or H ₂ O ₂ Can be manufactured. Molybdenum compounds prepared by reacting ammonium-containing molybdates with hydroxy compounds such as organic primary or secondary alcohols, glycols or phenols are described in U.S. Patent Nos. 3,784,482 and 3,787,329 to Cavitt. Have been.

Further, in U.S. Pat.No. 3,573,226 to Sorgenti, molybdenum powder is unreacted tert-butyl hydroperoxide and has a molecular weight of about 200-300,
It is disclosed that molybdenum-containing epoxidation catalyst solutions can be prepared by heating with a mixed stream containing a polyvalent compound having 4 to 6 hydroxyl groups per molecule. These catalysts are used for the epoxidation of propylene according to U.S. Pat. No. 3,666,777 to Sorgenti.

No. 3,953,362 to Lines et al. Describes a novel molybdenum epoxidation by reacting an oxygen-containing molybdenum compound with hydrogen peroxide and amines, and optionally water or alkylene glycol at elevated temperatures. It is disclosed that a catalyst can be produced. U.S. Patent No. 4,00, also to Lines et al.
According to No. 9,122, an oxygen-containing molybdenum compound is
Similar catalysts are prepared by reacting with amines and alkylene glycols at elevated temperatures.

The US patent to Mattucci et al. Also relates to a molybdenum glycol catalyst made from molybdenum acetylacetonate and isolated as a solid. If the material is used as an epoxidation catalyst, it must be used in solution with a hydrocarbon solvent. A molybdenum derivative compound that is also useful as an epoxidation catalyst is Hags
Molybdenum acetylacetonate, molybdic acids, according to U.S. Pat.No. 3,991,090 to trom et al.
And an oxygen-containing molybdenum compound such as molybdenum oxide and an organic compound having a vicinal hydroxyl group in the presence of a hydrohalic acid such as hydrofluoric acid and hydrochloric acid. Can be manufactured.

"Synthesis of Molybdenum / Alkylene Glycol Complex (Synthesis of Mol
ibdenum / Alkylene Glycol Complexes Useful as Epoxid
ation Catalysts), Mar 2, December 1986
In U.S. Pat.No. 4,626,596 to Quis et al., substantially, alkylene glycols, such as undiluted propylene glycol, and ammonia-containing molybdenum compounds, such as undiluted ammonium heptamolybdate tetrahydrate And a mixture of 7 to 20 moles of alkylene glycol per gram atom of molybdenum is heated to 80 to 130 ° C. in the presence of a small amount of water, and then the reaction product is heated under mild conditions. A method for making a catalytically active molybdenum complex by stripping to provide a molybdenum complex having a final moisture content of about 0.5-6% by weight is disclosed.

Marquis et al. Filed on December 6, 1985 and is reviewing “Synthesis of Molybdenum Oxide / Alkanol Comp.
U.S. Pat. No. 4,654,427, entitled "2-ethyl-1-hexanol", by a process starting in the presence of an aqueous ammonium hydroxide solution and carried out at 120 DEG C. to 190 DEG C. for 3 to 8 hours. C ₆ -C ₁₃ is reacted with molybdenum oxide, such as an alkanol molybdenum trioxide, ammonia and water substantially completely removed to generate a liquid molybdenum / alkanol complex dissolved in unreacted alkanol such as A method for obtaining a reaction product is disclosed.

Marquis et al. Filed December 6, 1985, entitled Synthesis of Ammonium Molybdate / Alkanol Complexe.
s) "and entitled U.S. Patent No. 4,650,886 includes a C ₆ -C ₁₃ alkanols, such as control of 2-ethyl-1-hexanol, molybdate such as ammonium heptamolybdate tetrahydrate Ammonium is reacted in the presence of water under atmospheric pressure at a temperature of 120 to 190 ° C. for 3 to 8 hours, and the generated ammonia and water are substantially completely removed. %, And a process for obtaining a liquid reaction product comprising a molybdenum / alkanol complex dissolved in unreacted alkanol.

There is still a need for an epoxidation catalyst that is stable, easy to manufacture, and has a high molybdenum content.

SUMMARY OF THE INVENTION The present invention provides an ammonium-containing molybdenum compound and an alkylene glycol under reduced pressure at about normal temperature (for example, 25
C.) to about 150 ° C. or less.

In the U.S. Pat.No. 4,626,596 to Marquis et al., The ratio of alkylene glycol reactant to molybdenum compound is determined by the ease with which the resulting reaction mixture can pass and the resulting complex solution being clear for extended periods of time. Improved methods of making molybdenum / alkylene glycol complexes are disclosed, based in part on the discovery that they affect the stability of keeping solids free. It has also been found that the actual origin of the molybdenum complex preparation is crucial in determining whether the resulting complex is good or bad when ultimately used as an epoxidation catalyst. Further, when a molybdenum complex produced from EG (ethylene glycol) or PG (propylene glycol) is used as an epoxidation catalyst, if the reaction temperature is too high, the molybdenum content in the complex becomes low and the solid content becomes large. It must not be too high (165-180 ° C) as it is formed. Also, in order for the complex to be useful as an epoxidation catalyst, without distilling off glycol,
A high molybdenum content must be achieved by adjusting the ratio of glycol to gram atoms of molybdenum. If the molybdenum content of the complex is increased by distilling off the glycol, the water content of the complex becomes too low, the selectivity based on the organic hydroperoxide consumed is reduced, and the action as an epoxidation catalyst is poor. Become something. A preferred method of U.S. Pat.No.4,626,596 is to set the ratio of the number of moles of glycol to the number of gram atoms of molybdenum in the range of 8: 1 to 16: 1,
Obtaining a reaction mixture substantially free of solids after aging for 1 hour at ~ 120 ° C. Next, vacuum stripping is performed so that the bottom residue becomes 80 to 95% by weight of the supplied material to remove water, ammonia, and the like.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the present invention, ammonium dimolybdate and an excess of ethylene glycol are mixed in a reaction vessel at room temperature and pressure, and then simultaneously with the pressure in the reaction vessel. Is reduced to about 5 to about 150 mmHg, while removing generated reaction by-products at the same time as the formation, while stirring, at room temperature (for example, 25 ° C) to about 15 mmHg.
Heat to 0 ° C. for about 5 to about 60 minutes, then return the reaction mixture to ambient temperature and pressure to obtain a dissolved molybdenum content of about
A substantially clear reaction product comprising a solution of molybdenum / ethylene glycol complex in unreacted ethylene glycol having 10 to about 15% by weight molybdenum and containing about 0.5 to about 5% by weight water. It has been found that a laminar flow depressurized production process including each step of recovering can rapidly and effectively produce a molybdenum / ethylene glycol complex substantially identical to the molybdenum / ethylene glycol complex of Marquis et al., US Pat. No. 4,626,596. Was issued. Preferably, the mixture is brought to a pressure of about
Heat under pressure of 10 to about 80 mmHg to 25 to 120 ° C over about 10 to 50 minutes and hold at this temperature for about 4 to 25 minutes. More preferably, the mixture is heated at 25-100 ° C under a pressure of about 15-60 mmHg.
Heat for 15-40 minutes and hold at this temperature for about 6-20 minutes.

The molybdenum starting material according to the present invention is ammonium dimolybdate.

Ethylene glycol is another coreactant used to make the molybdenum complex of the present invention.

The ratio of glycol to gram atoms of molybdenum in ammonium dimolybdate (moles of ethylene glycol) is important in determining the amount of molybdenum present in the final complex and the ease of processing.

For the ethylene glycol / ammonium dimolybdate system of the present invention, the preferred reactant ratio is 7: 1 expressed as moles of ethylene glycol to gram atoms of molybdenum in the ammonium dimolybdate compound.
~ 20: 1. A particularly preferred ratio of moles of glycol to gram atoms of molybdenum is 9: 1 to 11: 1. To obtain the best complex in terms of molybdenum content, ease of processing and storage stability, the proportion of water remaining in the complex must be in the range of 0.5-5% by weight. The reaction temperature for producing the complexes of the present invention must be between about 25-150 ° C, preferably between 25-120 ° C, and the final pressure is between about 5 and about 100 mmHg, more preferably between about 10 and about 80 mmHg. Must be under reduced pressure.

The pressure of the reaction mixture must be reduced while heating the reaction mixture to the desired final temperature, and this step must be performed in about 5 to about 60 minutes, more preferably about 10 to about 50 minutes. It was not necessary to increase the retention time of the reaction mixture at the final temperature, and a retention time of 7 to 13 minutes was found to be adequate (see Examples 1, 2 and 3). In general, no excess is necessary for the best complexes of the present invention. The amount of complex at the bottom of the tower is
Sufficient overhead distillate is removed during the reaction to reach 85-95% by weight, and the water content of the catalyst is preferably in the range 0.5-5.0% by weight. Especially for epoxidation applications, the water content of the final complex should generally be between about 1 to 3% by weight.

The reaction mixture obtained by the above-described method is a clear, substantially solid-free solution in which the molybdenum / ethylene glycol complex is dissolved in unreacted ethylene glycol, and can be recovered and used without excess. it can. The solution has a dissolved molybdenum content of about 10
It is a storage-stable, catalytically active substance having a water content of about 0.5 to 5.0% by weight. When prepared by suitable operating methods, the solution usually contains about 11% molybdenum.
-14% by weight and about 1-3% by weight of water, comprising about 90-92% by weight of the total weight of the feed.

The molybdenum / ethylene glycol complex of the present invention is titrated as an acid, despite having no additional free acidic groups such as carboxylic acid groups, so its use as an acid catalyst component is similar. Conceivable.
For example, the complex can be used as a useful cyclization catalyst for dissociating water, such as in the production of tetrahydrofuran from 1,4-butanediol and the production of triethylenediamine from hydroxyethylpiperazine. The complexes of the present invention can be prepared by hydroxylation, such as the production of resorcinol from toluene in the presence of hydroperoxide, carbonate formation from olefins, carbon dioxide and hydroperoxides, and from hydrocarbons and organic hydroperoxides. Can be used as a catalyst for the production of oxygenates.
Other catalytic uses for these complexes include:
In addition to those mentioned above, mention may be made of condensation, dehydration, esterification, oligomerization, polymerization, disproportionation and rearrangement. Molybdenum / glycol complexes can also be tried as corrosion inhibitors in antifreeze formulations and as direct additives to oils, greases and other lubricating fluids.

The molybdenum / ethylene glycol solution of the present invention is very suitable for use as an epoxidation catalyst. Prior to adding the epoxidation reaction mixture, usually the complex catalyst solution is premixed with one of the reactants, usually a hydroperoxide such as a solution of t-butyl hydroperoxide (TBHP) in t-butyl alcohol (TBA).

It is well known that solubilized molybdenum complexes effectively catalyze the epoxidation of propylene to propylene oxide in the presence of t-butyl hydroperoxide. The alkylene glycol / molybdenum complex of the present invention surprisingly provides a selectivity to propylene oxide on the order of 98-99% at a TBHP conversion of about 98-98.4%, while at the same time providing a propylene dimer Minimizes body formation and extremely low methyl formate formation.

Epoxidation is usually performed by reacting an olefin with an organic hydroperoxide in the presence of a catalyst and a solvent. Preferably, the olefin is propylene and the hydroperoxide is TBHP. With these reactants, the desired products are propylene oxide (PO) and t-butyl alcohol.

The concentration of the catalyst is preferably between 200 and 600 ppm based on the sum of the olefin and the organic hydroperoxide. Further, the reaction is carried out at 50-180 ° C, preferably 90-140 ° C,
Particularly preferably, it should be carried out at a temperature in the range of about 100-130 ° C. This reaction temperature is relatively low compared to other commercial methods. Another unusual feature is that the preferred molar ratio of olefin to hydroperoxide is very low, on the order of about 0.9: 1 to 3.0: 1.

Another preferred embodiment of the epoxidation consists in carrying out the reaction in a two-stage reaction in which the reaction times are approximately equal and the first stage is carried out at a lower temperature than the second stage. For example, the first hour of the reaction is preferably performed at a temperature in the range of 50-120 ° C and the second last hour of the reaction is carried out at about 120-150 ° C.
Perform in.

The present invention is further described by the following examples, which are provided for illustrative purposes and do not limit the scope of the invention.

Examples Example 1: Ratio of moles of EG / gram atoms of molybdenum = 9/1, total production time = 20 minutes (6032-25) equipped with magnetic stirrer, thermometer, K-head and condenser In a 500 ml round bottom flask, add 191.6 g (3.0
903 mol) and 58.4 g of ammonium dimolybdate (AD
M, molybdenum 0.3435 grams atom) was added. The ratio of the number of moles of EG to the number of gram atoms of molybdenum was 9/1. The stirrer was started, and heating was started. At 9:15 (25 ° C.), heating was started at a reduced pressure of 30 mmHg. At 9:27 (after 12 minutes), the temperature reached 100 ° C. (degree of reduced pressure: 40 mmHg). The reaction mixture was pale yellow and slightly solid. Heating at 100 ° C. was continued for at least 8 minutes until the reactants were clear and free of solids (vacuum reduced from 40 mmHg to 25 mmHg). Heating was stopped. The reaction mixture was clear and free of solids upon cooling. The preparation of the catalyst took a total of only 20 minutes from heating to the end of the reaction. The weight of the overhead in the receiving flask is 16.5 g (35.5% moisture) and the weight of the cold trap is
The amount was 1.4 g (water content: 87.5%). Product weight 227.2g
(90.88% of the filling amount). The product is molybdenum 1
4.0% (measured by atomic absorption method), water 2.27% (Karl Fisc
her method), N ₂ 1.10% (measured by the Kjeldahl method), and an acid value of 168.17 mg KOH / g of sample.

Example 2: Ratio of moles of EG / gram atoms of molybdenum = 10/1, total production time = 23 minutes (6032-24) In a flask equipped with each apparatus as described in Example 1, EG196. 2 g (3.16452 mol) and 53.8 g ADM (0.3165 gram atom molybdenum) were added. The ratio of the number of moles of EG to the number of gram atoms of molybdenum was 10.0 / 1. The stirrer was started and heating and depressurization were started simultaneously. 7:55 am
When the heating is started in a minute (23 ° C), the reaction mixture is slightly
The temperature reached 100 ° C. in 10 minutes (degree of reduced pressure: 40 mmHg). The reaction mixture was pale yellow and had some solids. Heating to 100
After a further 13 minutes at 0 ° C., the vacuum was reduced from 40 mmHg to 25 mmHg and the reaction mixture was clear and had no solids. The catalyst preparation took only a total of 23 minutes from the start of heating to cooling. The weight of the top distillate is 15.7g (37.9% moisture)
Met. The weight of the cold trap was 1.6 g (89.83% moisture). Product weight was 228.1 g (91.24% of charge). The product is molybdenum 13.2%, water 1.06% and N ₂
It had an acid number of 159.24 mg KOH / g of sample.

Example 3: Ratio of moles of EG / gram atoms of molybdenum = 11/1, total production time = 20 minutes (6032-26). In a flask equipped with each apparatus as described in Example 1, EG200. 1 g (3.2274 mol) and ADM 49.9 g (molybdenum)
0.2935 grams atom). The ratio of the number of moles of EG to the number of gram atoms of molybdenum was 11.0 / 1. The stirrer was started and heating and decompression started at 10:40 AM (24 ° C). At 10:53 am, the reaction mixture reached 100 ° C. (35 mmHg vacuum) (13 minutes have passed since the start of heating). The reaction mixture was kept at 100 ° C. for a further 7 minutes while reducing the pressure from 35 mmHg to 30 mmHg. At this point, the reaction mixture was cooled, confirming that no solids were present. The time required for heating and reaction was a total of 20 minutes. The weight of the overhead distillate was 14.9 g (37.68% moisture). The weight of the cold trap was 1.2 g (87.47% moisture). The product weight was 229.7 g. The product was molybdenum 11.8% (measured by atomic absorption method), water 2.81% and N ₂
It had an acid value of 140.65 mg KOH / g of sample.

Comparative Example 1: Ratio of mole number of EG / gram atom number of molybdenum = 9/1, solid content remained, total production time = 175 minutes (5990-31) Mechanical stirrer, thermometer, nitrogen inlet, K-head To a 500 ml round bottom flask equipped with a condenser and receiving flask were added 191.6 g (3.0903 mol) of EG and 58.4 g of ammonium dimolybdate (ADM, 0.3435 g atom of molybdenum). The ratio of the number of moles of EG to the number of gram atoms of molybdenum was 9/1. At 8:00 am, the reactants were added to the flask and heating started. Filled with nitrogen under atmospheric pressure. At 8:20 am the reaction mixture reached 100 ° C. and the color was milky (20 minutes had elapsed). 100 reaction mixture
The temperature was kept at 1.0 ° C for 1.0 hour (solid content remained until 9:20 am), cooled to 60 ° C (10:35 am), and at this point, vacuum suction was performed (35 mmHg), and the temperature was raised to 100 ° C. At 10:47 am and the reaction mixture reached 100 ° C. (4
The reaction mixture was kept at 100 ° C. under reduced pressure (45 mm Hg) for a further 8 minutes (until 10:55 am). At this point, the catalyst preparation was cooled and found to be clear and free of solids. 2 hours from initial heating to cooling of preparation 55
It took a minute (175 minutes). The top distillate weighs 9.5 g (moisture 4
9.85%). The weight of the cold trap is 1.0 g (moisture 92.4
24.7%) and the product weighs 234.7 g (93.88
%)Met. Analysis of the product indicated that molybdenum 13.5
%, A N ₂ 1.21%, 2.32% water, 164.91Mg per sample 1g
It was confirmed that it had an acid value of KOH.

Comparative Example 2: mole ratio of EG / gram atom number of molybdenum = 10/1, total production time = 100 minutes (5990-38) In a flask equipped with each device as described in Example 4, EG196. 2 g (3.164 mol) and ADM 53.80 g (molybdenum)
0.3165 grams atom). The ratio of the number of moles of EG to the number of gram atoms of molybdenum was 10/1. 10:55 am
In minutes, the reactants were added to the flask and heating started (atmospheric pressure, filled with nitrogen). At 11:10 am, the reaction mixture reached 100 ° C. (15 minutes passed), heating at 100 ° C. was continued for 1.0 hour (until 12:10 pm), then cooled quickly to 85 ° C. in 5 minutes ( The total elapsed time was 1 hour and 20 minutes). The reaction mixture was then reheated to 100 ° C. under reduced pressure (starting at 45 mm Hg) and reached 100 ° C. in just 10 minutes (30 mm Hg), which was kept at 100 ° C. under reduced pressure (30 mm Hg) for 10 minutes and then cooled. . No solids were present. The last cooling started at 12:35 pm. It took 1 hour and 40 minutes (100 minutes) for the manufacturing process from the start of heating to cooling. The overhead weight is 13.6 g (water content
49.39%), and the weight of the cold trap is 1.9 g (moisture 92.96%).
%)Met. The product weighs 229.9 g (91.96 filling
%)Met. The product was analyzed to be molybdenum 13.2
%, N ₂ 1.07%, water 1.54%, 156.81 mg per 1 g of sample
It was confirmed that it had an acid value of KOH.

Comparative Example 3: The ratio of the number of moles of EG / the number of gram atoms of molybdenum = 11/1, the total production time = 118 minutes (5990-47). In a flask equipped with each apparatus as described in Example 4, EG200. 12 g (3.228 mol) and 49.88 g ADM (0.3074 gram atom molybdenum) were added. The molar ratio of EG to molybdenum gram atoms was 11.0 / 1. 7:35 am
Minutes, add the reactants to the flask and start heating (23 ° C,
Nitrogen filling, under atmospheric pressure). At 7:55 am the reaction mixture was 10
When the temperature reached 0 ° C (20 minutes passed), it was kept at 100 ° C for 1.0 hour (8:55 am), and then immediately cooled to 65 ° C (15 minutes required, the time was 9:10 am T). A vacuum was applied at 65 ° C. (35 mmHg) and heating was started (9:10 am).
After about 13 minutes, the reaction mixture reached 100 ° C. (9:23 am
Min), the degree of pressure reduction was 25 mmHg. The reaction mixture was heated to 100 ° C (2
5mmHg) for another 10 minutes and observe (9:33 am
Min), the absence of solids was noted and finally cooled. The total production time from initial heating to cooling was 1 hour 58 minutes (118 minutes). The weight of the overhead distillate is 14.3 g
(Water content 40.50%) and the weight of the cold trap was 1.9 g (water content 91.93%). The product weighed 229.2 g (91.68% of charge) and was analyzed for molybdenum 11.
9% (analyzed by atomic absorption method, theoretical value = 12.29%), N ₂ 0.
It was confirmed to have 92% and 1.24% water and to have an acid value of 143.44 mg KOH / g of sample.

Claims (3)

(57) [Claims] 1. The method of claim 1, wherein (a) the molar ratio of ethylene glycol to gram atoms of molybdenum ranges from 7: 1 to 20: 1. Ammonium dimolybdate, which is not diluted specifically, is mixed in a reaction vessel at normal temperature and normal pressure. (B) The mixture is stirred for 5 to 60 minutes while removing volatile reaction by-products. During the same time, the pressure is 5-150mmHg
(C) then returning the reaction mixture to room temperature and normal pressure to produce a catalyst containing 10 to 15% by weight of molybdenum and substantially free of solids. A method for producing a catalytically active molybdenum complex, comprising recovering a solution in which molybdenum / ethylene glycol complex is dissolved in unreacted ethylene glycol. 2. The ratio of the number of moles of ethylene glycol to the number of gram atoms of molybdenum in the reaction starting mixture is 9;
The reaction mixture is kept at a pressure of 15-60 mmHg for 15-40 minutes at the same time.
The reaction mixture is heated to a temperature of 25 to 100 ° C. while being reduced to a normal temperature, and then the reaction mixture is returned to normal temperature and normal pressure. The overhead product from which reaction products generated are removed constitutes 8 to 10 wt% of the raw material mixture. The method of claim 1 wherein the final product comprises 11-14% molybdenum. (A) a substantially undiluted amount of ethylene glycol and substantially undiluted ethylene glycol in a molar ratio such that the ratio of the number of moles of ethylene glycol to the number of gram atoms of molybdenum ranges from 7: 1 to 20: 1; Preparing a feed mixture by mixing the undiluted ammonium dimolybdate in a reaction vessel at a temperature of 20-30 ° C. and atmospheric pressure; (b) evaporating the feed mixture While removing the product, the pressure is simultaneously increased to 10 to 80 for 10 to 50 minutes under stirring.
heating to a temperature of 25-150 ° C. while reducing to mmHg, (c) subjecting the mixture to the unreacted ethylene glycol for 2-30 minutes at the temperature and reduced pressure conditions set in step (b). Holding the complex for a time sufficient to complete the complex formation reaction, as indicated by the formation of a dissolved, solids-free solution; (d) then returning the reaction mixture to the starting temperature and pressure; (E) recovering a substantially solids-free, catalytically active, molybdenum / ethylene glycol complex dissolved in unreacted ethylene glycol having a molybdenum content of 10 to 15% by weight; In the step (e), the recovery complex comprises 88 to 95% by weight of the raw material mixture and contains 1 to 3% by weight of water. Manufacturing method of a molybdenum complex.