Acid-resistant alloy catalyst

Abstract

Disclosed is an acid-resistant alloy catalyst comprising nickel, one or more rare earth elements, stannum and aluminum. The acid-resistant alloy catalyst is low-cost and stable, and does not need a carrier, and can be stably used in continuous industrial production, thus achieving a low production cost.

Claims

1. A composite catalyst comprising (i) an acid-resistant alloy catalyst consisting essentially of, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin and 5-9 parts aluminium and (ii) a cocatalyst consisting of a soluble tungstic acid salt and/or an insoluble tungsten compound.

2. A composite catalyst comprising (i) an acid-resistant alloy catalyst consisting essentially of, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin, 5-9 parts aluminium and 1-90 parts tungsten and (ii) a cocatalyst consisting of a soluble tungstic acid salt and/or an insoluble tungsten compound.

3. A composite catalyst comprising (i) an acid-resistant alloy catalyst consisting essentially of, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin, 5-9 parts aluminium, 1-90 parts tungsten and 0.5-20 parts molybdenum and (ii) a cocatalyst consisting of a soluble tungstic acid salt and/or an insoluble tungsten compound.

4. A composite catalyst comprising (i) an acid-resistant alloy catalyst consisting essentially of, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin, 5-9 parts aluminium, 1-90 parts tungsten, 0.5-20 parts molybdenum, and 0.01-5 parts boron or phosphorus and (ii) a cocatalyst consisting of a soluble tungstic acid salt and/or an insoluble tungsten compound.

5. The composite catalyst of claim 1, wherein the rare earth elements are a collective term for 17 chemical elements, with atomic numbers 21, 39 and 57-71, in group IIIB of the periodic table.

6. The composite catalyst of claim 1, wherein the cocatalyst is a soluble tungstic acid salt selected from the group consisting of ammonium tungstate, sodium tungstate, sodium phosphotungstate and a combination thereof.

7. The composite catalyst of claim 1, wherein the cocatalyst is an insoluble tungsten compound selected from the group consisting of tungsten trioxide, tungstic acid and a combination thereof.

8. The composite catalyst of claim 2, wherein the cocatalyst is a soluble tungstic acid salt selected from the group consisting of ammonium tungstate, sodium tungstate, sodium phosphotungstate and a combination thereof.

9. The composite catalyst of claim 2, wherein the cocatalyst is an insoluble tungsten compound selected from the group consisting of tungsten trioxide, tungstic acid and a combination thereof.

10. The composite catalyst of claim 3, wherein the cocatalyst is a soluble tungstic acid salt selected from the group consisting of ammonium tungstate, sodium tungstate, sodium phosphotungstate and a combination thereof.

11. The composite catalyst of claim 3, wherein the cocatalyst is an insoluble tungsten compound selected from the group consisting of tungsten trioxide, tungstic acid and a combination thereof.

12. The composite catalyst of claim 4, wherein the cocatalyst is a soluble tungstic acid salt selected from the group consisting of ammonium tungstate, sodium tungstate, sodium phosphotungstate and a combination thereof.

13. The composite catalyst of claim 4, wherein the cocatalyst is an insoluble tungsten compound selected from the group consisting of tungsten trioxide, tungstic acid and a combination thereof.

Description

DESCRIPTION OF THE ACCOMPANYING DRAWINGS

(1) FIG. 1 is a schematic diagram of the process flow when the acid-resistant alloy catalyst of the present invention is used in the one-step catalytic hydrocracking of soluble sugar to prepare diols.

(2) FIG. 2 is a graph of the variation of ethylene glycol yield with time in embodiment 2.

PARTICULAR EMBODIMENTS

(3) The present invention is explained further below in conjunction with the accompanying drawings and embodiments.

Embodiment 1

(4) Preparation of Acid-Resistant Alloy Main Catalyst:

(5) With regard to the acid-resistant alloy catalyst of the present invention, an active metal powder with a high specific surface area can be prepared directly by chemical reduction or electrolytic deposition; alternatively, a metal alloy is first formed by smelting, then metal powder is formed by mechanical pulverizing or atomizing, etc., and finally, an active metal powder is formed by a conventional Raney nickel catalyst activation method. For example, in parts by weight, 10-90 parts, 1-5 parts, 1-60 parts, 5-9 parts, 1-90 parts, 0.5-20 parts and 0.01-5 parts of nickel, rare earth element, tin, aluminium, tungsten, molybdenum, and boron or phosphorus respectively are added to a smelting furnace; the temperature is raised to 1500-2000 C., then the temperature is lowered, and after thorough mechanical stirring to achieve uniformity, the furnace is emptied, to obtain the metal alloy. A hammer grinder is used to pulverize the metal alloy into metal powder, which is then immersed for 1-2 hours in a 20 wt %-25 wt % aqueous sodium hydroxide solution at 70-95 C., to form an active metal powder with a high specific surface area.

(6) An acid-resistant alloy catalyst Ni80La1Sn30Al5 (indicating that the composition of the acid-resistant alloy catalyst is 80 parts Ni+1 part La+30 parts Sn+5 parts Al, likewise below), an acid-resistant alloy catalyst Ni10Sm5Sn3Al9W70Mo5, an acid-resistant alloy catalyst Ni70Ce1Sn50Al7W5Mo1B5, an acid-resistant alloy catalyst Ni90Ce3Sn60Al9W20Mo5B1, an acid-resistant alloy catalyst Ni10Sm5Sn10Al9W90, an acid-resistant alloy catalyst Ni90Ce3Sn60Al9W20Mo20P0.01, and an acid-resistant alloy catalyst Ni80La1Ce0.5Sn30Al5 are prepared separately.

Embodiment 2

(7) 6 L of water and 1000 g of acid-resistant alloy catalyst Ni80La1Sn30Al5 (as a main catalyst) are added to a 10 L reaction kettle while stirring. The reaction kettle is sealed, hydrogen is passed in for 5 hours at 1000 L/h at atmospheric pressure to replace air in the reaction kettle, then the hydrogen pressure is raised to 10 MPa, and hydrogen is passed in for a further 5 hours, the reaction kettle temperature is raised to 250 C., and continuous feeding begins. The feed composition is: 50 wt % glucose, 2 wt % sodium tungstate, 48 wt % water, and the density of the sugar solution is about 1.23 g/cm.sup.3; the feed rate is 3 L/h. The residence time of sugar in the reaction kettle is 2 hours. Acetic acid is added to the reaction kettle such that the reaction system pH is 3.5. Reaction liquid and hydrogen after the reaction flow out of the reaction kettle through a filter into a condensing tank; the output speed of reaction liquid is 3 L/h, and reaction liquid is discharged from the bottom of the condensing tank after cooling, to give effluent. The effluent enters a rectification separation system, and water, ethylene glycol, propylene glycol, glycerol and sorbitol and sodium tungstate are respectively obtained, wherein heavy components that are not distilled out, including glycerol and sorbitol and sodium tungstate, are returned to the reaction system to react in a cycle. A sample is taken at the bottom of the condensing tank, and the composition thereof is detected by high performance liquid chromatography.

(8) A conventional technique may be used for the high performance liquid chromatography detection. The present invention provides the following experimental parameters for reference:

(9) Instrument: Waters 515 HPLC Pump;

(10) detector: Water 2414 Refractive Index Detector;

(11) chromatography column: 300 mm7.8 mm, Aminex HPX-87H ion exchange column;

(12) mobile phase: 5 mmol/L sulphuric acid solution;

(13) mobile phase flow rate: 0.6 ml/min;

(14) column temperature: 60 C.;

(15) detector temperature: 40 C.

(16) Results: the glucose conversion rate is 100%; the diol yield is 77%, wherein the ethylene glycol yield is 71%, the propylene glycol yield is 7%, and the butylene glycol yield is 3%; the methanol and ethanol yield is 5%, and other yields are 14%.

(17) FIG. 1 is a schematic diagram of the process flow when the acid-resistant alloy catalyst of the present invention is used in the one-step catalytic hydrocracking of soluble sugar to prepare diols.

(18) FIG. 2 is a graph of the variation of ethylene glycol yield with reaction system operation time. It can be seen from the figure that the ethylene glycol yield is substantially maintained at about 70%. This indicates that the composite catalyst can ensure that the ethylene glycol yield is still stable after 500 hours of continuous operation of the reaction system.

(19) When the reaction system pH is changed to 9, the results are: the glucose conversion rate is 100%; the diol yield is 68%, wherein the ethylene glycol yield is 38%, the propylene glycol yield is 27%, and the butylene glycol yield is 3%; the methanol and ethanol yield is 5%, and other yields are 27%.

Embodiment 3

(20) The acid-resistant alloy catalyst is Ni10Sm5Sn3Al9W70Mo5, and the amount added is 5000 g.

(21) The feed composition is: 15 wt % glucose, 0.01 wt % ammonium tungstate, 84.9 wt % water, and the density of the sugar solution is about 1.06 g/cm.sup.3.

(22) Reaction system pH=6.

(23) Other operating conditions are the same as in embodiment 2.

(24) Results: the glucose conversion rate is 100%; the diol yield is 66%, wherein the ethylene glycol yield is 61%, the propylene glycol yield is 3%, and the butylene glycol yield is 2%; the methanol and ethanol yield is 9%, and other yields are 25%.

Embodiment 4

(25) The acid-resistant alloy catalyst is Ni70Ce1Sn50Al7W5Mo1B5, and the amount added is 500 g.

(26) The amount of tungsten trioxide added is 100 g.

(27) The feed composition is: 40 wt % glucose, 60 wt % water, and the density of the sugar solution is about 1.18 g/cm.sup.3.

(28) Reaction system pH=4.2.

(29) Other operating conditions are the same as in embodiment 2.

(30) Results: the glucose conversion rate is 100%; the diol yield is 70%, wherein the ethylene glycol yield is 67%, the propylene glycol yield is 2%, and the butylene glycol yield is 1%; the methanol and ethanol yield is 9%, and other yields are 21%.

Embodiment 5

(31) The acid-resistant alloy catalyst is Ni90Ce3Sn60Al9W20Mo5B1, and the amount added is 1000 g.

(32) The feed composition is: 15 wt % xylose, 40 wt % glucose, wt % maltose, 1 wt % maltotriose, 1 wt % sodium phosphotungstate, 42 wt % water, and the density of the sugar solution is about 1.22 g/cm.sup.3.

(33) Reaction system pH=4.8.

(34) Other operating conditions are the same as in embodiment 2.

(35) Results: the conversion rate of xylose, glucose, maltose and maltotriose is 100%; the diol yield is 75%, wherein the ethylene glycol yield is 60%, the propylene glycol yield is 11%, and the butylene glycol yield is 4%; the methanol and ethanol yield is 7%, and other yields are 18%. After 500 hours of catalyst operation, the ethylene glycol yield is still stable.

Embodiment 6

(36) The acid-resistant alloy catalyst is Ni90Ce3Sn60Al9W20Mo5B1, and the amount added is 5000 g.

(37) The feed composition is: 50 wt % xylose, 0.1 wt % sodium tungstate, 49.9 wt % water, and the density of the sugar solution is about 1.21 g/cm.sup.3.

(38) Reaction system pH=4.8.

(39) Other operating conditions are the same as in embodiment 2.

(40) Results: the conversion rate of xylose is 100%; the diol yield is 67%, wherein the ethylene glycol yield is 49%, the propylene glycol yield is 16%, and the butylene glycol yield is 2%; the methanol and ethanol yield is 12%, and other yields are 21%. After 500 hours of catalyst operation, the ethylene glycol yield is still stable.

Embodiment 7

(41) The acid-resistant alloy catalyst is Ni10Sm5Sn10Al9W90, and the amount added is 180 g.

(42) The feed composition is: 60 wt % glucose, 2 wt % sodium tungstate, 38 wt % water, and the density of the sugar solution is about 1.29 g/cm.sup.3.

(43) The reaction pressure is 12 MPa, and the reaction temperature is 260 C.

(44) Other operating conditions are the same as in embodiment 2.

(45) Results: the conversion rate of glucose is 100%; the diol yield is 75%, wherein the ethylene glycol yield is 65%, the propylene glycol yield is 7%, and the butylene glycol yield is 3%; the methanol and ethanol yield is 11%, and other yields are 14%.

Embodiment 8

(46) The acid-resistant alloy catalyst is Ni90Ce3Sn60Al9W20Mo20P0.01, and the amount added is 5 g.

(47) The feed composition is: 5 wt % glucose, 0.05 wt % sodium tungstate, 94.95 wt % water, and the density of the sugar solution is about 1.02 g/cm.sup.3.

(48) Reaction system pH=1.

(49) The reaction pressure is 6 MPa, and the reaction temperature is 180 C.

(50) Other operating conditions are the same as in embodiment 2.

(51) Results: the conversion rate of glucose is 100%; the diol yield is 65%, wherein the ethylene glycol yield is 53%, the propylene glycol yield is 9%, and the butylene glycol yield is 3%; the methanol and ethanol yield is 4%, and other yields are 31%.

Embodiment 9

(52) The acid-resistant alloy catalyst is Ni80La1Ce0.5Sn30Al5; other operating conditions are the same as in embodiment 2.

(53) Results are similar to those of embodiment 2.

Embodiment 10

(54) The acid-resistant alloy main catalyst is Ni70Sm1Sn10Al7W5Mo0.5, and the amount added is 1500 g.

(55) The feed composition is: 40 wt % glucose, 60 wt % water, 0.5 wt % sodium tungstate, and the density of the sugar solution is about 1.18 g/cm.sup.3.

(56) Reaction system pH=4.2.

(57) Other operating conditions are the same as in embodiment 2.

(58) Results: the conversion rate of glucose is 100%; the diol yield is 87%, wherein the ethylene glycol yield is 80%, the propylene glycol yield is 5%, and the butylene glycol yield is 2%; the methanol and ethanol yield is 3%, and other yields are 10%.

(59) Clearly, the abovementioned embodiments of the present invention are merely examples given to explain the present invention clearly, and by no means define the embodiments of the present invention. A person skilled in the art could make other changes or modifications in different forms on the basis of the explanation above. It is not possible to list all embodiments here exhaustively. All obvious changes or modifications extended from the technical solution of the present invention shall still fall within the scope of protection of the present invention.