Method of preparation of a copper-containing catalyst for liquid - phase dehydrogenation of alcohols

 

(57) Abstract:

Usage: the process of liquid-phase dehydrogenation of one - and polyhydric alcohols, aliphatic and alicyclic series. The catalyst was prepared by treatment of the aqueous complex solution of copper with a solution of sodium borohydride or potassium in the ratio of 2 moles of borohydride per 1 mol of copper. Time effective operation of the catalyst is increased 10 times. table 4.

The invention relates to the production of a catalyst containing copper, which can be used in the processes of liquid-phase dehydrogenation of one - and polyhydric alcohols, aliphatic and alicyclic series.

A known method of producing a catalyst containing copper, intended for liquid-phase dehydrogenation of dialkylglycerol /Pat. USA N 2 807 629, 1957/ accepted us as a prototype.

The catalyst is prepared as follows.

An aqueous solution containing ammonium bichromate and ammonium hydroxide, is mixed with an aqueous solution of nitrates of copper in the ratio of 1 mol of copper in 0.5 mol of ammonium bichromate. The precipitation of chromate copper is separated and dried to remove moisture. Dry chromate copper heat up to 350-500oWith received CMV acetic acid, washed and dried.

The catalyst is dispersed powder containing copper and chromium. For the process of liquid-phase dehydrogenation catalyst suspendered in dialkylglycerol and the mixture is heated to boiling at atmospheric pressure. Working temperature of the process 240-280oC.

The most effective metrogroove catalyst for liquid-phase dehydrogenation of diethylene glycol.

Disadvantages metrogroove catalyst are:

1. Limited time effective operation of the catalyst.

2. A multi-stage preparation process, including not less than ten operations.

3. The need for special equipment for crushing and heating to 500oC.

4. Disposal of spent catalyst requires a special technology that allows you to separate the copper from chrome.

The objective of this invention to provide a catalyst containing copper, for liquid-phase dehydrogenation of one - and polyhydric alcohols, aliphatic and alicyclic series, which has long uptime.

The problem is solved by a method of producing a catalyst containing the or of sodium borohydride or potassium in the ratio of 2 moles of borohydride per 1 mol of copper. The precipitation was separated, washed and dried.

Received the proposed method, the catalyst in the reaction liquid-phase dehydrogenation of one - and polyhydric alcohols aliphatic series has uptime is 10 times greater compared to the prototype.

The method is illustrated by the following examples.

Example 1.

In a reaction vessel with a volume of 1.5 liters, equipped with a magnetic stirrer, is placed 1.0 l of ammonia solution of copper containing 50 g (0.2 mol) of copper sulfate pativedha and 80 ml of aqueous 25% ammonia, and 15.2 g (0.4 mol) of sodium borohydride dissolved in 100 ml of distilled water, the resulting solution is added to the ammonia solution of copper with continuous stirring.

The precipitation is separated on a filter, washed and air-dried at 100-110oC.

The end product of the number 12,45 g (yield of copper to 98.5%) is a free-flowing powder, stable in air.

Examples 2, 3 differ in that the catalyst is obtained from tartrates and tilantongo solutions of copper, the data shown in table 1.

Similar results were obtained using potassium borohydride. The data are shown in table 2 (examples 4-6).

The process of dehydrogenation is carried out as follows: into a reaction vessel connected with a distillation column, download the alcohol and catalyst, the mixture is heated to boiling at atmospheric pressure, while continuously distilled liquid reaction products.

Example 7

106 g of diethylene glycol and 1.5 g of the catalyst obtained by the proposed method from the ammonia solution of copper by the action of sodium borohydride is loaded into the reactor with a volume of 250 ml Reactor is connected with a distillation column, which in turn is connected with a water cooler.

The mixture is heated to boiling at atmospheric pressure, the product of the dehydrogenation of 2-para-dioxanone continuously removed from the reactor. For 225 minutes received 85,43 g distillate containing 96% mass 2-pair-of dioxanone, 82% yield of theoretical.

The temperature of the reaction mixture at the beginning of the process 240oWith, in the end - 260oC.

Examples 8, 9, 10, characterized in that the dehydration was exposed to 1,4-butanediol, nonanol-1 and cyclohexanol, are shown in table 3.

Similar results were obtained when using the catalyst obtained is I, of ammonia, tartrates, talantova solutions using potassium borohydride.

Data on time, efficient operation of the catalyst obtained for a process of liquid-phase dehydrogenation of diethylene glycol in the reactor of periodic action. The operating time of the catalyst net time dehydrogenation, excluding auxiliary operations. The results are shown in table 4.

The data show that the inventive catalyst can be used in the processes of liquid-phase dehydrogenation of alcohols. Time effective operation of the catalyst is more than ten times longer than the effective work metrogroove catalyst.

Method of preparation of a copper-containing catalyst for liquid-phase dehydrogenation of alcohols, including deposition from aqueous solution and drying, characterized in that the deposition is carried out on the aqueous complex solution of copper with a solution of sodium borohydride or potassium in the ratio of 2 moles of borohydride per 1 mol of copper.

 

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FIELD: catalyst manufacture technology.

SUBSTANCE: invention relates to carbon monoxide-water steam conversion to form nitrogen-hydrogen mixture that can be used in ammonia synthesis. Preparation of catalyst comprises precipitation of iron hydroxide from iron nitrate solution with ammonia-containing precipitator, washing of iron hydroxide to remove nitrate ions, mixing with copper compound, granulation, and drying and calcination of granules. Invention is characterized by that iron hydroxide is mixed with copper and calcium oxides at molar ratio Fe2O3/CuO/CaO = 1:(0.03-0.2):(1.0-2.0), after which mechanical activation is performed. Resulting catalyst is 1.8-2.0-fold stronger and by 11.0-15.4% more active than prototype catalyst.

EFFECT: increased strength and catalytic activity.

1 tbl, 3 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention provides catalyst for production of glyoxal via catalytic oxidation of ethylene glycol, wherein lower catalyst bed is composed of crystalline copper, upper bed of fibrous silver granules, and the two beds are modified with phosphorus. Crystalline copper particles are 1 to 100 μm in pore size and 5 to 50 μm in wall thickness. Fibrous silver granules are 0.01 to 3.00 mm in size with their specific surface being between 0.10 and 0,17 m2/g. Surface concentration of phosphorus is between 0.1 and 6% for lower bed and between 0.05 and 3.00% for upper one.

EFFECT: increased conversion and selectivity of ethylene glycol oxidation process and simplified catalyst bed formation.

4 cl, 4 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

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