Acid-resistant alloy catalyst

Abstract

An acid-resistant alloy catalyst, comprising nickel, one or more rare earth element, tin, aluminum and molybdenum. The catalyst is cheap and stable, does not need a carrier, can be stably applied in industrial continuous production, and can lower the production cost.

Claims

1. An acid-resistant alloy catalyst, characterized in that the acid-resistant alloy catalyst comprises nickel, one or more rare earth element, tin, aluminum and molybdenum, wherein the catalyst does not contain tungsten.

2. The acid-resistant alloy catalyst as claimed in claim 1, characterized in that the acid-resistant alloy catalyst comprises, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin, 5-9 parts aluminum and 0.1-20 parts molybdenum.

3. The acid-resistant alloy catalyst as claimed in claim 1, characterized in that the acid-resistant alloy catalyst comprises nickel, one or more rare earth element, tin, aluminum, molybdenum and boron or phosphorus.

4. The acid-resistant alloy catalyst as claimed in claim 3, characterized in that the acid-resistant alloy catalyst comprises, in parts by weight, 10-90 parts nickel, 1-5 parts rare earth element, 1-60 parts tin, 5-9 parts aluminum, 0.1-20 parts molybdenum and 0.01-5 parts boron or phosphorus.

5. The acid-resistant alloy catalyst as claimed in claim 1, characterized in that the rare earth element is a general designation for 17 chemical elements with atomic numbers 21, 39 and 57-71 in group IIIB of the periodic system.

Description

DESCRIPTION OF THE ACCOMPANYING DRAWINGS

(1) Particular embodiments of the present invention are explained in further detail below in conjunction with the accompanying drawings.

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

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

PARTICULAR EMBODIMENTS

(4) In order to explain the present invention more clearly, the present invention is explained further below in conjunction with preferred examples and the accompanying drawings. Those skilled in the art should understand that the content described in specific terms below is explanatory and non-limiting, and should not be used to limit the scope of protection of the present invention.

Example 1

(5) Preparation of Acid-Resistant Alloy Catalyst:

(6) For the acid-resistant alloy catalyst of the present invention, chemical reduction or electrolytic deposition may be used to directly prepare an active metal powder having a high specific surface area, or smelting is used first of all to form a metal alloy, then mechanical pulverizing, atomization, etc. are used to form a metal powder, and finally a conventional Raney nickel catalyst activation method is used to form an active metal powder. For example, nickel, a rare earth element, tin, aluminum, molybdenum and boron or phosphorus are added to a smelting furnace in the following parts by weight: 10-90 parts, 1-5 parts, 1-60 parts, 5-9 parts, 0.1-20 parts and 0.01-5 parts respectively; the temperature is increased to 1500-2000° C., then lowered; after thorough mechanical stirring to achieve uniformity, a metal alloy exits the furnace and is obtained. A hammer mill is used to pulverize the metal alloy to a metal powder, and the metal powder is immersed in a 20 wt %-25 wt % aqueous solution of sodium hydroxide for 1-2 hours at 70-95° C., to form an active metal powder having a high specific surface area.

(7) The following are prepared: an acid-resistant alloy catalyst Ni80Sm1Sn30Al8Mol (meaning that the composition of the acid-resistant alloy catalyst is 80 parts Ni+1 part Sm+30 parts Sn+8 parts Al+1 part Mo, likewise below), an acid-resistant alloy catalyst Ni10Sm5Sn3Al2Mo5, an acid-resistant alloy catalyst Ni70Ce1Sn50Al7Mo0.5B5, an acid-resistant alloy catalyst Ni90Ce3Sn60Al9Mo20P0.01 and an acid-resistant alloy catalyst Ni80La1Ce0.5Sn30Al7Mo10.

Example 2

(8) 6 L of water and 1400 g of the acid-resistant alloy catalyst Ni80Sm1Sn30Al8Mol (as the main catalyst) are added to a 10 L reaction kettle while stirring. The reaction kettle is sealed, and hydrogen is passed in at 1000 L/h at atmospheric pressure to replace air in the reaction kettle for 5 hours, then the hydrogen pressure is increased to 10 MPa, and hydrogen continues to be passed in for 5 hours, the reaction kettle temperature is increased to 250° C., and continuous feeding is begun. The feed composition is: 40 wt % glucose, 0.5 wt % sodium tungstate, 59.5 wt % water, with a sugar solution density of about 1.17 g/cm.sup.3; the feeding 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 4.4. Hydrogen and reaction liquid resulting from the reaction flow out of the reaction kettle through a filter and enter a condensing tank, the discharge rate of the reaction liquid being 3 L/h; the reaction liquid is cooled and then discharged from the bottom of the condensing tank, and a liquid effluent is obtained. The liquid effluent enters a rectification separation system; water, ethylene glycol, propylene glycol, glycerol and sorbitol as well as sodium tungstate are obtained separately, wherein a heavy component that is not distilled out, including glycerol and sorbitol as well as sodium tungstate, returns to the reaction system to react cyclically. A sample is taken at the bottom of the condensing tank, and high-efficiency liquid chromatography is used to detect the composition thereof.

(9) High-efficiency liquid chromatography detection may use conventional technology. The present invention provides the following experimental parameters for reference:

(10) apparatus: Waters 515 HPLC Pump;

(11) detector: Water 2414 Refractive Index Detector; chromatography column: 300 mm×7.8 mm, Aminex HPX-87H ion exchange column;

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

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

(14) column temperature: 60° C.;

(15) detector temperature: 40° C.

(16) The results are as follows: glucose conversion is 100%; the diol yield is 85.9%, wherein the ethylene glycol yield is 78%, the propylene glycol yield is 6% and the butanediol yield is 2.1%; the yield of methanol and ethanol is 3.7%, and other yields are 10.4%.

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

(18) FIG. 2 is a graph of the variation of ethylene glycol yield with reaction system operating time. It can be seen from the figure that the yield of ethylene glycol substantially remains at about 78%. This indicates that the composite catalyst can ensure that after 500 hours of continuous operation of the reaction system, the yield of ethylene glycol is still stable.

Example 3

(19) The acid-resistant alloy catalyst is Ni10Sm5Sn3Al2Mo5, and the amount added is 1400 g.

(20) The feed composition is: 40 wt % glucose, 2 wt % sodium tungstate, 48 wt % water, with a sugar solution density of about 1.17 g/cm.sup.3.

(21) Reaction system pH=6.

(22) Other operating conditions are the same as in example 2.

(23) The results are as follows: glucose conversion is 100%; the diol yield is 62.4%, wherein the ethylene glycol yield is 25.4%, the propylene glycol yield is 30.4% and the butanediol yield is 6.6%; the yield of methanol and ethanol is 9.4%, and other yields are 28.2%.

Example 4

(24) The acid-resistant alloy catalyst is Ni70Ce1Sn50Al7Mo0.5B5, and the amount added is 500 g. 100 g of tungsten trioxide is added.

(25) The feed composition is: 60 wt % glucose, 40 wt % water, with a sugar solution density of about 1.29 g/cm.sup.3.

(26) Reaction system pH=4.2.

(27) Other operating conditions are the same as in example 2.

(28) The results are as follows: glucose conversion is 100%; the diol yield is 20.8%, wherein the ethylene glycol yield is 10.9%, the propylene glycol yield is 7.5% and the butanediol yield is 2.4%; the yield of methanol and ethanol is 15.6%, and other yields are 63.6%.

Example 5

(29) The acid-resistant alloy catalyst is Ni90Ce3Sn60Al9Mo20P0.01, and the amount added is 1000 g.

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

(31) Reaction system pH=4.8.

(32) Other operating conditions are the same as in example 2.

(33) The results are as follows: conversion of xylose, glucose, maltobiose and maltotriose is 100%; the diol yield is 71.6%, wherein the ethylene glycol yield is 65.5%, the propylene glycol yield is 4.3% and the butanediol yield is 1.8%; the yield of methanol and ethanol is 3.4%, and other yields are 25%. After 500 hours of operation of the catalyst, the yield of ethylene glycol is still stable.

Example 6

(34) The acid-resistant alloy catalyst is Ni80La1Ce0.5Sn30Al7Mo10, and the amount added is 5000 g.

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

(36) Reaction system pH=4.8.

(37) Other operating conditions are the same as in example 2.

(38) The results are as follows: xylose conversion is 100%; the diol yield is 72.1%, wherein the ethylene glycol yield is 58.8%, the propylene glycol yield is 12.4% and the butanediol yield is 0.9%; the yield of methanol and ethanol is 6.9%, and other yields are 21%. After 500 hours of operation of the catalyst, the yield of ethylene glycol is still stable.

Example 7

(39) The acid-resistant alloy catalyst is Ni80Sm1Sn30Al8Mol, and the amount added is 1400 g.

(40) The feed composition is: 40 wt % sucrose, 1 wt % sodium tungstate, 59 wt % water, with a sugar solution density of about 1.18 g/cm.sup.3.

(41) Reaction system pH=4.7.

(42) Other operating conditions are the same as in example 2.

(43) The results are as follows: sucrose conversion is 100%; the diol yield is 81.7%, wherein the ethylene glycol yield is 52.6%, the propylene glycol yield is 24% and the butanediol yield is 5.1%; the yield of methanol and ethanol is 3.3%, and other yields are 15%. After 500 hours of operation of the catalyst, the yield of ethylene glycol is still stable.

(44) Clearly, the above examples of the present invention are merely examples given in order to clearly explain the present invention, and do not limit the embodiments of the present invention. Other changes or modifications in different forms may still be made on the basis of the description above. It is not possible to exhaustively list all embodiments here. All obvious changes or modifications derived from the technical solution of the present invention still fall within the scope of protection of the present invention.