The method of synthesis chemical industrial raw material and high-octane fuel, and composition of the high-octane fuel

 

(57) Abstract:

The invention relates to methods for production of 1-butanol (options), 1,3-butadiene and high-octane fuel from ethanol. All methods include contacting ethanol with nizkoglikemichesky calcium phosphate having a specific area of at least 2 m2/year Method of synthesis of 1-butanol, as a rule, is carried out at a molar ratio of CA/P of 1.6 to 1.8 and a temperature varying from 350 to 450oAnd in a variant of the synthesis of 1-butanol nizkoglikemichesky calcium phosphate contains at least one type of metal and/or oxide of a metal selected from BA, Na, K, Li, Cs, Sr, Y, Ce, Sb, Eu, Ti, W and Zr in an amount of not more than 50 mol.% with respect to CA and having a molar ratio (CA + metal)/R from 1 to 2, at a temperature varying from 300 to 450oS. the Method of synthesis of 1,3-butadiene is usually carried out at a molar ratio of CA/P from 1.55V to 1.8 and a temperature varying from 450 to 700oWith, and the method of synthesis of high-octane fuel at a molar ratio of CA/P from 1.55V to 1.8 and a temperature varying from 300 to 700oS. 4 S. p. F.-ly, 3 ill., 8 table.

The technical field

The invention relates to a method of manufacturing chemical industrial raw material, high-calcium, carrying the metal.

Background of the invention

As is well known, in recent years there have been many attempts to obtain large quantities of chemical industrial raw materials with alcohols, in particular ethanol as a raw material instead of chemical industrial raw materials derived from oil.

The method of producing ethylene from ethanol as raw material, in which the catalyst is calcium phosphate, are known, but this method is characterized by low activity and the economically disadvantaged. As a method of dehydration of alcohol is known to use an acid catalyst on a solid carrier, such as zeolite, and so on, but in this way aluminum in the zeolite framework is released under the action of the water formed during the reaction, which leads to a decrease in the activity of the catalyst, and this method cannot be used in the industry for a long period of time.

A known method of producing acetaldehyde from ethanol using calcium phosphate or calcium phosphate, bearing metals, such as Cu, Ni, and so on , but its activity and selectivity are low, and this method of ecostore on a solid medium such as a catalyst of the platinum group on the media, MgO, etc. but there are problems in the dispersion characteristics of the impurities and stability.

As a way to obtain diethyl simple ether from ethanol is known to use an acid catalyst on a solid carrier, such as zeolite, and so on, but the aluminum in the zeolite framework is released under the action of the water formed during the reaction, which leads to lowering of catalytic activity and the catalyst cannot be used for a long period of time.

As a method of producing 1,3-butadiene from ethanol offers a method using as a catalyst Al2O3ZnO (6:4) [S. K. Bhattcharyya and N. O. Ganguly; J. Appl. Chem.; 12, 105 (1962)] and the method of using a thick adsorbed metal (Mn, V, Mo, W, etc.) (Japanese patent application 178281/1980 and 157814/1981). However, in the first method, there are complexities associated with obtaining stable catalyst and thermal stability of the catalyst, and the second method leads to a run-level mass production, and thus, in the manner of problems from the standpoint of mass production. Accordingly 1,3-butadiene main floor, acetaldehyde way, way rape and so on, but these methods are complex and inefficient. Japanese patent publication 305238/1993 discloses a method of producing hydrocarbon base gasoline from lower alcohols using a catalyst formed on the basis of calcium phosphate bearing metal.

Disclosure of the invention

The aim of the present invention is to develop a production method for the effective production of chemical industrial raw materials such as ethylene, acetaldehyde, diethyl simple ether, 1-butanol, 1,3-butadiene, and so on, high-octane fuel and its mixture with the use of ethanol as the starting material.

The result of detailed studies of the method of obtaining chemical industrial raw materials such as ethylene, acetaldehyde, diethyl simple ether, 1-butanol, 1,3-butadiene, etc. and high-octane fuel, and so on, when using ethanol as the source material on the basis of advantageous from the industrial point of view the method in the present invention it has been found that the above objective can be achieved by using a catalyst based on calcium phosphate.

Brief description of the invention

Fig.1 represents the definition powder

Fig. 2 is an image showing the reaction apparatus used in the example according to the invention

Fig. 3 is a view showing the dependence of the reaction time of the catalyst is subjected to repeated regeneration, and conversion to ethanol.

The best way of carrying out the invention

Hereinafter the invention is described in detail. It is known that calcium phosphate is hydroxyapatite [CA10(RHO4)6(OH)2] , triphosphate calcium [CA3(RHO4)2], calcium hydrogen phosphate [San(RHO4(from 0 to 2) H2O] diphosphate calcium (Ca2P2O7), dihydrophosphate achocalla [CA8H2(RHO4)65H2O], tetracaine phosphate [CA4(RHO4)2O], amorphous calcium phosphate [CA3(RHO4)2mo2O], etc.

Hydroxyapatite is usually present above the stoichiometric composition, but its properties are such that even if the composition does not meet this stoichiometric composition, the hydroxyapatite may have the structure of Apatite. The hydroxyapatite with the same stoichiometric composition can be presented on the basis of [CA10-z(NRA4)z(PO4)Restore and after stirring the mixture for one day, the mixture was dried at 140oC. the Dried product was grinded and was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mole % aluminum.

(Sample 2)

The solution obtained by dissolving 232,3 g of calcium nitrate [CA(NO3)24H2A] 5.0 liters of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere, and the mixture was stirred for one day. After that, the product was collected via filtration, washed with water and dried at 140oWith to obtain a powder having a molar ratio of CA/P of 1.65. After dissolution 0,037 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, 10.0 g of the above powder of calcium phosphate was added to the solution followed by stirring for one day, the mixture was dried at 140oWith, grinded and was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mole % Al with respect to CA and having a molar relation is SUB>)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere, followed by stirring for one day. In addition, the solution obtained by dissolution of 0.67 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water was added to the above mixture and the resulting mixture was stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding the dried product is milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,0.

(Sample 4)

After a light grinding in a mortar calcium phosphate having a molar ratio of CA/P of 1.50, a solution obtained by dissolution of 0.67 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water was added to the powder and then the mixture was stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding imicheskogo composition, containing 3 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,50.

(Sample 5)

The solution obtained by dissolving 22,53 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere, followed by stirring for one day. In addition, the solution obtained by dissolution of 0.67 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water was added to the above mixture and the resulting mixture was additionally stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,65.

(Sample 6)

The solution obtained by dissolving 27,31 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 the target ammonia, having established pH from 9 to 11, in nitrogen atmosphere, followed by stirring for one day. In addition, the solution obtained by dissolution of 0.67 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water was added to the above mixture and the resulting mixture was additionally stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 2,00.

(Sample 7)

The baking powder synthesized using the same procedure as in the case of sample 5, in air at 750oC for 2 hours was obtained powdery catalyst composition containing 3 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,65.

(Sample 8)

The solution obtained by dissolution of 11.61 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water was added on kavanian in one day. In addition, a solution obtained by dissolving 19,73 g of aluminum nitrate [Al(NO3)3N2O] in 500 ml of distilled water was added to the above mixture and the resulting mixture was additionally stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 50 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,65.

(The reference sample 1)

After a light grinding in a mortar calcium phosphate having a molar ratio of CA/P of 1.00, milled product was annealed in air at 700oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 2)

After a light grinding in a mortar calcium phosphate having a molar ratio of CA/P 1,50, milled product was annealed in air at 700oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 3)

The solution obtained by dissolving 232,3 g of calcium nitrate [CA(NO3)24H2A] 5.0 l of distilled water,J. water was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere, followed by stirring for one day. Then the product was separated by filtration, washed with water, dried at 140oWith and were annealed in air at 700oC for 2 hours to obtain a powder, for example, comparison with the molar ratio CA/P of 1.65.

(The reference sample 4)

After a light grinding in a mortar calcium phosphate having a molar ratio of CA/P 2,00, milled product was annealed in air at 700oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 5)

After dissolution 0,037 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, 10 g of the powder of the comparison sample 3 was added to the solution followed by stirring for one day, the mixture was dried at 140oFrom and after drying were annealed in air at 700oC for 2 hours to obtain a powder sample comparison, containing 0.03 mol % of aluminum.

(The comparison sample 6)

Sample 5 was evaluated at the reaction temperature 350oC.

(The reference sample 7)

The powder obtained powder reference sample. The sample was evaluated at the reaction temperature of 750oC.

(The reference sample 8)

Sample 8 was evaluated at the reaction temperature 350oC.

(The reference sample 9)

The powder obtained using the synthesis method of sample 8 was annealed in air at 800oC for 2 hours to obtain a powder sample comparison. The sample was evaluated at the reaction temperature of 750oC.

[Evaluation of catalytic characteristics]

Each prepared sample of the samples 1 to 8 samples and comparisons 1 to 9 was formed into tablets from #14 to #26. Then 0.6 ml of tablets were Packed in a quartz tube and conducted preliminary processing in the case of the sample, not of bearing metal, process heating (dehydration) in gas-carrier (1% Ar/No basis: flow rate of 80 CC/min) at 500oC for 30 minutes in the case of the sample carrying metal processing recovery of contained metal in 20% H2(He basis: flow rate of 100 CC/min) at 500oC for 30 minutes.

After this pre-treatment the reaction was carried out under the conditions of the concentration of ethanol 20%, flow rate of carrier gas 80 CC/min (total flow rate of 100 CC/min) and spatial supatone from 400 to 700oC.

Identification of components of the reaction gas was measured using a mass spectrometer with a gas chromatograph (GC-MS) and measuring the ethanol conversion and selectivity of the synthesis gas was measured using a gas chromatograph (GC) (detector:FID), and they were determined using the following formula from the values of the peak area of each component.

Conversion of ethanol (%)= (1-(value of the peak area of ethanol after reaction)/(value of the peak area of ethanol after the reaction)X100

The selectivity of the synthesis gas (%)= (the value of the peak area)/(total peak area value of the peak area of residual ethanol)X100

Spatial time-out (UIP) was defined as the output (g) of hydrocarbons per 1 liter of catalyst and 1 hour and, considering hydrocarbons as CH2xn, the space time yield was calculated by the following formula.

Spatial time-out (g/(CL))=entered ethanol (mol)(214 conversion of ethanol selectivity/volume of catalyst.

As the reaction apparatus used catalytic reaction apparatus gas flow shown in Fig.2. The evaluation results are shown in table.1.

2) In the case of the catalyst of the synthesis of acetaldehyde:[CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, a solution obtained by dissolving 0,120 g of copper nitrate [Cu(NO3)23H2O] and 0,201 g of iron nitrate (III) [Fe(NO3)3N2O] in 50 ml of distilled water was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 0.5 mol % each of Cu and Fe in relation to CA and having the (Ca+Cu+Fe)/P molar ratio of 1.57.

(Sample 10)

The solution obtained by dissolving 19,71 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having, solutions obtained by dissolving each of the 2.46 g of copper nitrate [Cu(NO3)23H2O] and 4.15 g of iron nitrate (III) [Fe(NO3)3N2O] in 200 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 10 mol % each of Cu and Fe in relation to CA and having the (Ca+Cu+Fe)/P molar ratio of 1.75.

(Sample 11)

The solution obtained by dissolving 17,68 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11 in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of 2.21 g of copper nitrate [Cu(NO3)23H2O] and 3.72 g of iron nitrate (III) [Fe(NO3)3N2O] in 200 ml of distilled water, respectively, to OSHA at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 10 mol % each of Cu and Fe in relation to CA and having the (Ca+Cu+Fe)/P molar ratio of 1.57.

(Sample 12)

The solution obtained by dissolving 9,72 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of the 5,94 g of copper nitrate [Cu(NO3)23H2About] and 10,14 g of iron nitrate (III) [Fe(NO3)3N2About] in 500 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 28 mol % each of Cu and Fe on uranium 21,88 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of 0,096 g of copper nitrate [Cu(NO3)23H2O] 0,161 g of iron nitrate (III) [Fe(NO3)3N2O] and 0.075 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 0.4 mol % of Cu, and 0.4 mol % Fe and 0.2 mol % Al with respect to CA and having the (Ca+Cu+Fe+Al)/P molar ratio of 1.57.

(Sample 14)

The solution obtained by dissolving 16,57 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2Tion of pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of 2.21 g of copper nitrate [Cu(NO3)23H2About] , and 3.72 g of iron nitrate (III) [Fe(NO3)3N2About] and 1.77 g of aluminum nitrate [Al(NO3)2N2O] in 200 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 10 mol % Cu, 10 mol % Fe and 5 mol % Al with respect to CA and having the (Ca+Cu+Fe+Al)/P molar ratio of 1.57.

(Sample 15)

The solution obtained by dissolving 4,22 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of the 3, the waste of aluminum [Al(NO3)3N2O] in 500 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 28 mol % Cu, 28 mol % Fe and 14 mol % Al with respect to CA and having the (Ca+Cu+Fe+Al)/P molar ratio of 1.00.

(Sample 16)

The solution obtained by dissolving 6,63 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to the water

the ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of the 5,94 g of copper nitrate [Cu(NO3)23H2O], 10,14 g of iron nitrate (III) [Fe(NO3)3N2About] and 5,01 g of aluminum nitrate [Al(NO3)39H2O] in 500 ml of distilled water, respectively, was added to the solution, and then further re the product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 28 mol % Cu, 28 mol % Fe and 14 mol % Al with respect to CA and having the (Ca+Cu+Fe+Al)/P molar ratio of 1.57.

(Sample 17)

The solution obtained by dissolving 6,97 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of the 6,24 g of copper nitrate [Cu(NO3)23H2O], 10,66 g of iron nitrate (III) [Fe(NO3)3N2O] and of 5.26 g of aluminum nitrate [Al(NO3)3N2O] in 500 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 28 mol % Cu, 28 mol % Fe and 14 mole % Aristorenas 8,45 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of the EUR 7.57 g of copper nitrate [Cu(NO3)23H2O], 12,92 g of iron nitrate (III) [Fe(NO3)3N2About] and 6.38 g of aluminum nitrate [Al(NO3)3N2About] in 500 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 28 mol % Cu, 28 mol % Fe and 14 mol % Al with respect to CA and having the (Ca+Cu+Fe+Al)/P molar ratio of 2.00.

(Sample 19)

Sample 16 was evaluated at the reaction temperature 300oC.

(Sample 20)

Sample 16 was evaluated at the reaction temperature 200oC.

[Sample comparison]

(The sample compared the air at 500oC for 2 hours to obtain a powder sample comparison. The sample was evaluated at the reaction temperature 350oC.

(The comparison sample 11)

The solution obtained by dissolving 22,10 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition having a CA/P molar ratio of 1.57.

(The reference sample 12)

The powder obtained using the synthesis method of sample 3, was treated as the reference sample 3 was annealed in air at 500oC for 2 hours to obtain a powder sample comparison.

(The reference sample 13)

The powder obtained using the synthesis method of the comparison sample 4, was treated as the reference sample 4 was annealed in air at Astor, obtained by dissolving 22,04 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, the solutions obtained by dissolving each of the 0,023 g of copper nitrate [Cu(NO3)23H2O] , 0,038 g of iron nitrate (III) [Fe(NO3)3N2About] 0,018 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mol % of Cu, 0.1 mole % Fe and 0.05 mol % Al with respect to CA and having the (Ca+Cu+Fe+Al)/P molar ratio of 1.57.

(The reference sample 15)

The solution obtained by dissolving 17,68 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water, and race was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the resulting mixture was stirred for one day. In addition, a solution obtained by dissolving 4,320 g of copper nitrate [Cu(NO3)23H2O] in 200 ml of distilled water was added to the above solution and the mixture was stirred for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 500oC for 2 hours to obtain a powdery catalyst composition containing 20 mol % Cu with respect to CA and having the (CA+Cu)/P molar ratio of 1.57.

(The reference sample 16)

Sample 16 was evaluated at the reaction temperature 150oC.

(The reference sample 17)

Sample 16 was evaluated at the reaction temperature 500oC.

(The reference sample 18)

Used MgO (reagent), which was the usual basic solid media.

[Evaluation of catalytic characteristics]

Each prepared sample of specimens from 9 to 20 samples and comparison with 10 to 18 was formed into tablets from #14 to #26. Then for the sample conducted preliminary treatment as in the case of ethylene. After the flow of carrier gas 80 CC/min (total flow rate of 100 CC/min) and spatial velocity (GHSV) of 10,000 (l/h) at normal pressure.

In the case of the synthesis of acetaldehyde, the reaction temperature was in the range from 200 to 450oC. Identification and definition of the reaction gas is carried out as in the case of ethylene. As the reaction apparatus used catalytic reaction apparatus gas flow shown in Fig.2.

The evaluation results are shown in table.2.

3) In the case of catalyst for the synthesis of diethyl simple ether:

[Catalyst]

(Sample 21)

After a light grinding in a mortar calcium phosphate having a molar ratio of CA/P of 1.45, milled product was annealed at 700oC for 2 hours and grinded in a mortar to obtain a powder. After dissolution 0,037 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, 10 g of the above powder was added to the solution and after stirring the mixture for one day, the mixture was dried at 140oAnd the dried product was grinded and was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mole % aluminum.

(Sample 22)

After dissolution 0,037 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, 10 receiving in one day, the mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mole % aluminum.

(Sample 23)

Sample 22 was evaluated at the reaction temperature 400oC.

(Sample 24)

Using a light grinding in a mortar calcium phosphate having a molar ratio of CA/P of 1.00 was obtained powder. After the dissolution of 1.24 g of aluminum nitrate [Al(NO3)3N2O] in 200 ml of distilled water, 10 g of the above powder was added to the solution followed by stirring for one day, the mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 5 mol % Al with respect to CA and having a molar ratio (CA+Al)/P of about 1.0.

(Sample 25)

The solution obtained by dissolving 20,99 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution with the set R is th dissolution 1,77 g of aluminum nitrate [Al(NO3)3N2O] in 200 ml of distilled water was added to the above solution followed by stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 5 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,57.

(Sample 26)

The solution obtained by dissolving representing 22.06 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere, followed by stirring for one day. In addition, a solution obtained by dissolving 1.86 g of aluminum nitrate [Al(NO3)3N2O] in 200 ml of distilled water was added to the above solution followed by stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain the molar ratio (CA+Al)/P 1,65.

(Sample 27)

Using a light grinding in a mortar calcium phosphate having a molar ratio of CA/P 2,00 received powder. After dissolution 2,48 g of aluminum nitrate [Al(NO3)3N2O] in 200 ml of distilled water, 10 g of the above powder was added to the solution followed by stirring for one day, the mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 5 mol % Al with respect to CA and having a molar ratio (CA+Al)/P roughly 2.0.

(Sample 28)

The solution obtained by dissolving 11,05 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere, followed by stirring for one day. In addition, a solution obtained by dissolving 18,78 g of aluminum nitrate [Al(NO3)39H2O] in 500 ml of distilled water was added to the above solution followed by stirring for whom sbhe at 700oC for 2 hours to obtain a powdery catalyst composition containing 50 mol % of aluminum in relation to CA and having a molar ratio (CA+Al)/P 1,57.

(Sample 29)

Sample 28 was evaluated at the reaction temperature 350oC.

(Sample 30)

Sample 28 was evaluated at the reaction temperature 300oC.

(Sample 31)

Sample 28 was evaluated at the reaction temperature 200oC.

(The reference sample 19)

Used a reference sample 1.

(The reference sample 20)

The calcium phosphate of the comparison sample 11 was treated as in the reference sample 11 and was annealed in air at 700oC for 2 hours to obtain a powder for sample comparison.

(The reference sample 21)

Used a reference sample 3.

(The reference sample 22)

Used a reference sample 4.

(The reference sample 23)

After dilution to 0.011 g of aluminum nitrate [Al(NO3)3N2O] in 50 ml of distilled water, 10 g of the powder obtained in the synthesis method of the comparison sample 11 was added to the solution followed by stirring for one day, the mixture was dried at 140oFrom and after grinding is burned in air what is a high % of aluminum.

(The reference sample 24)

Sample 25 was evaluated at the reaction temperature 200oC.

(The reference sample 25)

Sample 25 was evaluated at the reaction temperature 450oC.

(The reference sample 26)

Sample 28 was evaluated at the reaction temperature 150oC.

(The reference sample 27)

Sample 28 was evaluated at the reaction temperature 450oC.

[Evaluation of catalytic characteristics]

Each prepared sample of the samples from 21 to 31 samples and comparison with 19 to 27 were formed into tablets from #14 to #26. Then the sample was performed pre-treatment, as in the case of ethylene.

After this pre-treatment the reaction was carried out under the conditions of the concentration of ethanol 20%, flow rate of carrier gas 80 CC/min (total flow rate of 100 CC/min) and spatial velocity (GHSV) of 10,000 (l/h) at normal pressure. In the case of synthesis of diethyl ether, the reaction temperature was in the range from 200 to 400oC. Identification and definition of the reaction gas was conducted using the same methods, as in the case of ethylene. As the reaction apparatus used catalytic reaction apparatus gas flow, shown is a:

[Catalyst]

(Sample 32)

The solution obtained by dissolving 225,2 g of calcium nitrate [CA(NO3)24H2O] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then this product was separated by means of filtration, washed with water and after drying at 140oWith, were annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition having a CA/P molar ratio of 1.60.

(Sample 33)

Used a reference sample 3.

(Sample 34)

The reference sample 3 was evaluated at the reaction temperature 400oC.

(Sample 35)

The reference sample 3 was evaluated at the reaction temperature 350oC.

(Sample 36)

The solution obtained by dissolving 239,3 g of calcium nitrate [CA(NO3)24H2O] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to e one day. Then this product was separated by means of filtration, washed with water and after drying at 140oC was annealed in air at 900oC for 2 hours to obtain a powdery catalyst composition having a CA/P molar ratio of 1.70.

(Sample 37)

The solution obtained by dissolving 253,4 g of calcium nitrate [CA(NO3)24H2A] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2NRA4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then this product was separated by means of filtration, washed with water and after drying at 140oC was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition having a CA/P molar ratio of 1.80.

(Sample 38)

After the dissolution of 1.24 g of cerium nitrate [CE(NO3)36N2O] in 200 ml of distilled water, 9,59 g of the powder obtained based on the method of synthesis of the comparison sample 3, was added to the solution followed by stirring for one day. Then the product was dried at 140oAnd pecheskago composition, containing 3 mol % of CE with respect to CA and having the (CA+CE)/P mol ratio of 1.65.

(Sample 39)

Sample 38 was evaluated at the reaction temperature 400oC.

(Sample 40)

Sample 38 was evaluated at the reaction temperature 350oC.

(Sample 41)

Sample 38 was evaluated at the reaction temperature 300oC.

(Sample 42)

The solution obtained by dissolving? 7.04 baby mortality g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, a solution obtained by dissolving 8,29 g of magnesium nitrate [Mg(NO3)26N2About] in 500 ml of distilled water was added to the above solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 50 mol % Mg compared kg calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, a solution obtained by dissolving 7,22 g of magnesium nitrate [Mg(NO3)26N2O] in 500 ml of distilled water was added to the above solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 30 mol % of Mg relative to CA and having the (CA+Mg)/P molar ratio of 1.50.

(Sample 44)

The solution obtained by dissolution of 11.61 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture paramasivan2O] in 500 ml of distilled water was added to the above solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 50 mol % of CE with respect to CA and having the (CA+CE)/P mol ratio of 1.65.

(Sample 45)

The solution obtained by dissolving 14,08 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, solutions obtained by dissolving each of 11,96 g of cerium nitrate [CE(NO3)36N2O] 9,18 and g of aluminum nitrate [Al(NO3)3N2O] in 500 ml of distilled water, respectively, was added to the above solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding sticheskogo composition, containing 30 mol % of CE and 20 mol % Al with respect to CA and having the (CA+CE+Al)/P molar ratio of 2.00.

(The reference sample 28)

Used a reference sample 1.

(The reference sample 29)

The solution obtained by dissolving 211,1 g of calcium nitrate [CA(NO3)24H2O] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then this product was separated by means of filtration, washed with water and after drying at 140oC was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition having a CA/P molar ratio of 1.50.

(The reference sample 30)

The calcium phosphate of the comparison sample 3 was treated, as in the case of example 3 comparison, and was annealed in air at 1200oC for 2 hours to obtain a powder sample comparison.

(The reference sample 31)

Used a reference sample 4.

(The reference sample 32)

The reference sample 3 was evaluated at a temperature of Rea is 500oC.

(The reference sample 34)

Sample 38 was evaluated at the reaction temperature 250oC.

(The reference sample 35)

Sample 38 was evaluated at the reaction temperature 500oC.

[Evaluation of catalytic characteristics]

Each prepared sample of the samples from 32 of 45 samples and comparison with 28 35 formed in the tablets from #14 to #26. Then the sample was performed pre-treatment, as in the case of ethylene.

After this pre-treatment the reaction was carried out under the conditions of the concentration of ethanol 20%, flow rate of carrier gas 80 CC/min (total flow rate of 100 CC/min) and spatial velocity (GHSV) of 10,000 (l/h) at normal pressure. In the case of the synthesis of 1-butanol, the reaction temperature was in the range from 300 to 450oC. Identification and definition of the reaction gas was conducted using the same methods, as in the case of ethylene. As the reaction apparatus used catalytic reaction apparatus gas flow shown in Fig.2.

The evaluation results are shown in table.4.

5) In the case of catalyst for the synthesis of 1,3-butadiene

[Catalyst]

(Sample 46)

Used on the 2, and was annealed in air at 1000oC for 2 hours to obtain a powdery catalyst composition.

(Sample 48)

The solution obtained by dissolving 228,0 g of calcium nitrate [CA(NO3)24H2A] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then this product was separated by means of filtration, washed with water and after drying at 140oC was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition having a CA/P molar ratio of 1.62.

(The reference sample 49)

Sample 48 was evaluated at the reaction temperature of 550oC.

(Sample 50)

Sample 48 was evaluated at the reaction temperature 500oC.

(Sample 51)

Sample 48 was evaluated at the reaction temperature 450oC.

(Sample 52)

Used a reference sample 3.

(Sample 53)

Calcium phosphate sample 36 was treated, as in the case of the sample 36, and then burned at vozrast 54)

Used the sample 37.

(Sample 55)

The solution obtained by dissolving 225,7 g of calcium nitrate [CA(NO3)24H2O] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then the product was collected by filtration, washed with water and dried at 140oWith to obtain powder. After dissolution 0,224 g of the chloride of zirconium (IV) (ZrCl4) in 100 ml of distilled water, to 9.91 g of the above powder was added to the solution followed by stirring for one day, the mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 1 mol % of Zr with respect to CA and having the (Ca+Zr)/P molar ratio of 1.62.

(Sample 56)

A sample of 55 were evaluated at the reaction temperature 450oC.

(Sample 57)

Used sample 2.

(Sample 58)

Sample 2 was evaluated at the reaction temperature 500oC.

(Sample 59)
3
)24H2O] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then the product was collected by filtration, washed with water and dried at 140oWith to obtain powder. After dissolution 0,847 g tetraisopropoxide titanium {[(CH3)2SNO]4Ti} in 100 ml of ethanol, 9,86 g of the above powder was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Ti with respect to CA and having the (Ca+Ti)/P mol ratio of 1.65.

(Sample 61)

After dissolution 0,715 g of tungstic acid (H2WO4) in 100 ml of distilled water, for 9.47 g of calcium phosphate synthesized in the sample 60, to the solution followed by stirring for one day. Then the mixture was dried at 140oFrom and after grinding was annealed in air at 700oWith over 2 hours for Poluchenie ratio of 1.65.

(Sample 62)

After dissolution 0,685 g of the chloride of zirconium (IV) (ZrCl4) in 100 ml of distilled water, 9,73 g of calcium phosphate synthesized in the sample 60, to the solution followed by stirring for one day. Then the mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % Zr with respect to CA and having the (Ca+Zr)/P mol ratio of 1.65.

(Example 63)

Used the sample 42.

(Sample 64)

Used a sample of 43.

(Sample 65)

The solution obtained by dissolution of 11.61 g of calcium nitrate [Ca(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, a solution obtained by dissolving 9,13 g of the chloride of zirconium (IV) (ZrCl4) in 500 ml of distilled water, respectively, was added to the above mixture, followed by additional stirring for one day. TheoC for 2 hours to obtain a powdery catalyst composition containing 50 mol % Zr with respect to CA and having the (Ca+Zr)/p mol ratio of 1.65.

(Sample 66)

The solution obtained by dissolving 14,08 g of calcium nitrate [Ca(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day.

In addition, the solutions obtained by dissolving each of 7.23 g of the chloride of zirconium (IV) (ZrCl4and 9,18 g of aluminum nitrate [Al(NO3)3)N2O] in 500 ml of distilled water, respectively, was added to the above mixture, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 30 mol % Zr and 20 mol % Al with respect to CA and having the (Ca+Zr+Al/P molar ratio of 2.00.

(The reference sample 36).

(The reference sample 38)

Calcium phosphate sample 48 was treated, as in the case of a sample of 48, and was annealed in air at 1200oC for 2 hours to obtain a powdery catalyst composition.

(The reference sample 39)

Used a reference sample 4.

(The reference sample 40)

Sample 48 was evaluated at the reaction temperature 400oC.

(The reference sample 41)

Calcium phosphate sample 48 was treated, as in the case of a sample of 48, and was annealed in air at 800oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 42)

A sample of 55 were evaluated at the reaction temperature 400oC.

(The reference sample 43)

Calcium phosphate sample 55 were treated, as in the case of a sample of 55, and was annealed in air at 800oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 44)

Sample 2 was evaluated at the reaction temperature 400oC.

(The reference sample 45)

Calcium phosphate sample 2 was treated as in the case of sample 2, and annealed in air at 800oC for 2 hours and grinded in a mortar to obtain a powder the product), mentioned in example of synthesis of 1,3-butadiene from ethanol.

[Evaluation of catalytic characteristics]

Each prepared sample of the samples from 46 to 66 samples and comparison with 36 46 formed in the tablets from #14 to #26. Then the sample was performed pre-treatment, as in the case of ethylene.

After this pre-treatment the reaction was carried out under the conditions of the concentration of ethanol 20%, flow rate of carrier gas 80 CC/min (total flow rate of 100 CC/min) and spatial velocity (GHSV) of 10,000 (l/h) at normal pressure. In the case of the synthesis of 1,3-butadiene synthesis was carried out at a temperature in the range from 450oWith up to 700oC. Identification and definition of the reaction gas was conducted using the same methods, as in the case of ethylene.

As the reaction apparatus used catalytic reaction apparatus gas flow shown in Fig.2.

The evaluation results are shown in table.5 and table.6.

6) In the case of catalyst for the synthesis of high-octane fuel:

[Catalyst]

(Example 67)

Used the sample 20.

(The reference sample 68)

Calcium phosphate sample 48 was treated, cnia powder sample comparison.

(Sample 69)

Used a sample of 48.

(Sample 70)

Used a reference sample 3.

(Sample 71)

The reference sample 3 was evaluated at the reaction temperature 400oC.

(Sample 72)

The reference sample 3 was evaluated at the reaction temperature 450oC.

(Example 73)

The reference sample 3 was evaluated at the reaction temperature 500oC.

(Sample 74)

The reference sample 3 was evaluated at the reaction temperature of 550oC.

(Sample 75)

Used a sample of 53.

(Sample 76)

Used the sample 37.

(Example 77)

The solution obtained by dissolving 228,0 g of calcium nitrate [CA(NO3)24H2A] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2HPO4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then the product was collected by filtration, washed with water and dried at 140oWith to obtain a powder having a molar ratio of CA/P of 1.62. After dissolution 0,007 g of lithium nitrate (LiNO3) in 100 ml distilleria the value of one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mole % Li in relation to CA and having the (Ca+Li)/P molar ratio of 1.62.

(Sample 78)

The solution obtained by dissolving 232,3 g of calcium nitrate [CA(NO3)24H2O] 5.0 l of distilled water and a solution obtained by dissolving 78,87 g of ammonium phosphate [(NH4)2NRA4] in 3.0 liters of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. Then the product was collected by filtration, washed with water and dried at 140oWith to obtain a powder having a molar ratio of CA/P of 1.65. After dissolution 0,029 g of Nickel nitrate (Ni(NO3)26N2O) in 100 ml of distilled water, 10.0 g of the above powder of calcium phosphate was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 0.1 mole % of Ni with respect to Sa and 3) in 100 ml of distilled water, 9,98 g unburnt powder of calcium phosphate synthesized in the sample, 48, was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % Li in relation to CA and having the (Ca+Li)/P molar ratio of 1.62.

(Sample 80)

Sample 79 evaluated at the reaction temperature 450oC.

(Sample 81)

Sample 79 evaluated at the reaction temperature 400oC.

(Sample 82)

After dissolution 0,838 g of Nickel nitrate [Ni(NO3)26N2O] in 100 ml of distilled water, 9,83 g unburnt powder of calcium phosphate synthesized in the sample 48, followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Ni with respect to CA and having the (Ca+Ni)/P molar ratio of 1.62.

(Example 83)

After dissolution 0,854 g of Nickel nitrate [Ni(NO3)26H2O] in 100 ml of distilled vivarium in one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 1000oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Ni with respect to CA and having the (Ca+Ni)/P mol ratio of 1.65.

(Example 84)

Ni-containing calcium phosphate obtained in the sample, 83, was treated, as in the case of a sample of 83, was annealed in air at 700oC for 2 hours and grinded in a mortar to obtain a catalytic composition.

(Example 85)

A sample of 84 were evaluated at the reaction temperature 400oC.

(Sample 86)

After dissolution 0,871 g of zinc nitrate [Zn(NO3)26N2On]

100 ml of distilled water, 9.81 g unburnt powder of calcium phosphate synthesized in the reference sample 3, was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Zn with respect to CA and having the (Ca+Zn)/P mol ratio of 1.65.

(Sample 87)

After dissolution 0,837 g tetraisopropoxide titanium {[(CH3)2SNO]4Ti} in restore, followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Ti with respect to CA and having the (Ca+Ti)/P mol ratio of 1.65.

(Sample 88)

After dissolution 0,616 g of strontium nitrate [Sr(NO3)2] in 100 ml of distilled water, 9,74 g unburnt powder of calcium phosphate synthesized in the reference sample 3, was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Sr relative to CA and having the (Ca+Sr)/P mol ratio of 1.65.

(Example 89)

After dissolution 1,274 g of europium nitrate [Eu(NO3)36N2O] in 100 ml of distilled water, of 9.56 g of unburnt powder of calcium phosphate synthesized in the reference sample 3, was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition, sod the following dissolution 0,483 g of cesium chloride (CsCl) in 100 ml of distilled water, being 9.61 g unburnt powder of calcium phosphate synthesized in the reference sample 3, was added to the solution followed by stirring for one day. The mixture was dried at 140oFrom and after grinding was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 3 mol % of Cs with respect to CA and having the (CA+Cs)/P mol ratio of 1.65.

(Example 91)

Used the sample 42.

(Example 92)

Used a sample of 43.

(Sample 93)

The solution obtained by dissolving 11,40 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, the solution obtained by dissolution of 3.99 g of lithium nitrate (LiNO3) in 500 ml of distilled water was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding ground product was burned on who is Aulnay % Li in relation to CA and having the (Ca+Li)/P molar ratio of 1.62.

(Example 94)

The solution obtained by dissolution of 11.61 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2NRA4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, a solution obtained by dissolving to 13.09 g of Nickel nitrate [Ni(NO3)26H2O] in 500 ml of distilled water was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 50 mol % of Ni with respect to CA and having the (Ca+Ni)/P mol ratio of 1.65.

(Example 95)

The solution obtained by dissolving 11,96 g of calcium nitrate [CA(NO3)24H2About] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution, having a is obtained by dissolving 13,39 g of zinc nitrate [Zn(NO3)26N2About] in 500 ml of distilled water was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled product was annealed in air at 700oC for 2 hours to obtain a powdery catalyst composition containing 50 mol % Zn with respect to CA and having the (Ca+Zn)/P molar ratio of 1.70.

(Example 96)

The solution obtained by dissolving 14,08 g of calcium nitrate [CA(NO3)24H2O] in 500 ml of distilled water and a solution obtained by dissolving 7,89 g of ammonium phosphate [(NH4)2HPO4] in 300 ml of distilled water, was added dropwise to aqueous ammonia solution having a prescribed pH from 9 to 11, in nitrogen atmosphere and the mixture was stirred for one day. In addition, the solutions obtained by dissolving each of 9,85 g of Nickel nitrate [Ni(NO3)26N2O] 9,18 and g of aluminum nitrate [Al(NO3)3N2About] in 500 ml of distilled water, respectively, was added to the solution, followed by additional stirring for one day. Then the mixture was evaporated to dryness at 140oFrom and after grinding milled produk, containing 30 mol % Ni and 20 mol % Al with respect to CA and having the (Ca+Ni+Al)/P molar ratio of 2.00.

(The reference sample 47)

Used a reference sample 1.

(The reference sample 48)

Used a reference sample 29.

(The reference sample 49)

Used a reference sample 4.

(The reference sample 50)

The calcium phosphate of the comparison sample 3 was treated, as in the case of the comparison sample 3 was annealed in air at 1100oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 51)

The reference sample 3 was evaluated at the reaction temperature 300oC.

(The reference sample 52)

The calcium phosphate of the comparison sample 3 was treated, as in the case of the comparison sample 3 was annealed in air at 800oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 53)

Calcium phosphate sample 79 were treated, as in the case of a sample of 79, was annealed in air at 800oC for 2 hours and grinded in a mortar to obtain a powder sample comparison.

(The reference sample 54)

Ni-containing calcium phosphate obtained in education and in a mortar to obtain a catalytic composition.

(The reference sample 55)

Sample 82 evaluated at the reaction temperature 250oC.

(The reference sample 56)

Ni-containing calcium phosphate obtained in the sample, 82, was treated, as in the case of a sample of 82, was annealed in air at 800oC for 2 hours and grinded in a mortar to obtain a catalytic composition.

(The reference sample 57)

Zn-containing calcium phosphate obtained in the sample, 86, was treated as in sample 86, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 58)

Ti-containing calcium phosphate obtained in the sample of 87, was treated, as in the case of a sample of 87, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 59)

Sr-containing calcium phosphate obtained in the sample of 88, was treated, as in the case of a sample of 88, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 60)

Eu-containing calcium phosphate obtained in the sample of 89, was treated as in sample 89, and Sal is and.

(The reference sample 61)

Cs-containing calcium phosphate obtained in the sample 90, processed, as in the case of the sample 90, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 62)

Mg-containing calcium phosphate obtained in the sample 42, was treated, as in the case of the sample 42, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(Sample comparison 63)

Mg-containing calcium phosphate obtained in the sample, 43, was treated as in sample 43, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 64)

Li-containing calcium phosphate obtained in the sample, 93, worked, as in the case of a sample of 93, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 65)

Ni-containing calcium phosphate obtained in a sample of 94, was treated, as in the case of a sample of 94, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a rolled is, probatively, as in the case of a sample of 95, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

(The reference sample 67)

Ni, Al-containing calcium phosphate obtained in a sample of 96, was treated, as in the case of a sample of 96, and was annealed in air at 800oC for 2 hours, and grinded in a mortar to obtain a catalytic composition.

[Evaluation of catalytic characteristics]

Each prepared sample of the samples from 67 to 96 samples and comparison with 47 67 formed in the tablets from #14 to #26. Then the sample was performed pre-treatment, as in the case of ethylene.

After this pre-treatment the reaction was carried out under the conditions of the concentration of ethanol 20%, the concentration of methanol 20%, flow rate of carrier gas 80 CC/min (total flow rate of 100 CC/min) and spatial velocity (GHSV) of 10,000 (l/h) at normal pressure. In the case of synthesis of high-octane fuel synthesis was carried out at a reaction temperature in the range from 300 to 700oC. Identification and definition of the reaction gas was conducted using the same methods, as in the case of ethylene. As the reaction apparatus of the evaluation are shown in table.7 and table.8 below. In the table, the liquid fraction is a reaction gas, liquefied in pipe cooling at 0oC. evaluation of the liquid fraction was performed by the evaluation method of a liquid fraction JIS.

As an example, analysis of the composition of the liquid fraction below shows the analytical data for sample 74. The main components were oxygen-containing hydrocarbon compounds and their content was as follows.

Ethanol= 10% (unreacted ethanol), C4H10=6%, C4H8O=4%, C5H10O=3%, C6H14O=2%, C6H10=5%, aromatics=8% other hydrocarbons.

Components other liquid fractions formed during reactions using the catalysts of the examples were almost the same as the components in the sample 73, but the content of these components in these fuels was different depending on the type of catalyst and the reaction temperature.

After working for 12 hours when using 0.6 ml tablets #14 to # 26, formed from a sample of 73, under conditions of reaction temperature 500oC, the concentration of ethanol 20%, the spatial velocity (GHSV) of 10,000 (l/h), normal pressure, as processing for regeneration of the catalyst, the catalyst was treated in the 0oWith the EtOH concentration= 20%, GHSV= 10000 (l/h) and V=0.6 ml), was measured by the conversion of ethanol, whereby measured the stability of catalytic activity over time. The result is shown in Fig.3. The result shows that by periodic regeneration of the catalytic activity of the catalyst is fully preserved.

1. The method of synthesis of 1-butanol, characterized in that ethanol is introduced into contact with nizkoglikemichesky calcium phosphate having a specific area of at least 2 m2/g and a molar ratio of CA/P of between 1.6 to 1.8, at a temperature varying from 350 to 450oC.

2. The method of synthesis of 1,3-butadiene, wherein the ethanol is injected into contact with nizkoglikemichesky calcium phosphate having a specific area of at least 2 m2/g and a molar ratio of CA/P from 1.55V to 1.8, at a temperature varying from 450 to 700oC.

3. The method of synthesis of high-octane fuel, wherein the ethanol is injected into contact with nizkoglikemichesky calcium phosphate having a specific area of at least 2 m2/g and a molar ratio of CA/P from 1.55V to 1.8, at a temperature varying from 300 to 700oC.

4. The method of synthesis of 1-butanol, characterized in, Thu the metal and/or metal oxide, selected from BA, Na, K, Li, Cs, Sr, Y, Ce, Sb, Eu, Ti, W and Zr in an amount of not more than 50 mol.% in relation to Sa, and having a specific area of at least 2 m2/g and a molar ratio (CA+metal)/R from 1 to 2, at a temperature varying from 300 to 450oC.

 

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