WO2008071090A1

WO2008071090A1 - A catalyst for hydrocracking high alcohols, its preparation method and application

Info

Publication number: WO2008071090A1
Application number: PCT/CN2007/003593
Authority: WO
Inventors: Bo Ma
Original assignee: Bo Ma
Priority date: 2006-12-14
Filing date: 2007-12-14
Publication date: 2008-06-19
Also published as: CN101199930A

Abstract

A catalyst with metallic framework, its preparation method and application. The catalyst adopts Ni, Co and/or Cu as skeleton elements, one or more elements selecting from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, Zr, Mo, Ru, Re, Ir, Pt, Au, B, P, Se, Sn, Sb, La and Ce as promoters. The catalyst can be prepared by smelting process. The catalyst can be used for hydrocracking high alcohols such as sorbierite to lower alcohols. The catalyst has high activity, high selectivity and long life with chemical stability and physical stability under reaction condition.

Description

Cerium carbon polyol hydrocracking catalyst, preparation method and application thereof

The invention relates to a high carbon polyol hydrocracking catalyst, a preparation method and application thereof. Specifically, the catalyst can be used as a low carbon polyol for hydrocracking a high carbon polyol such as sorbitol prepared from a renewable raw material. Catalyst wherein the low carbon polyol is a low carbon polyol such as ethylene glycol, propylene glycol, glycerin, butanediol or pentanediol or various isomers thereof, or any two or more of them A multicomponent low carbon polyol mixture composed of a low carbon polyol. BACKGROUND OF THE INVENTION Low-carbon polyols such as ethylene glycol, propylene glycol, glycerol and butanediol have wide applications in petrochemicals and can be used as polyester materials, antifreeze agents, lubricants, plasticizers, surfactants, etc. Production of raw materials. For a long time, the industrial production methods and synthetic raw materials of low-carbon polyols depend on petroleum resources, and the cracking of petroleum through ethylene, propylene epoxidation and hydration processes, long route, many by-products, and serious pollution. In recent years, high-carbon polyols such as sorbitol and xylitol obtained by using cheap biological resources have good economical efficiency by one-step hydrogenation catalytic cracking to synthesize low-carbon polyols. The by-products are methanol, ethanol or propanol. Etc., less pollution, becoming the most challenging route in the production of low carbon polyols (see US6841085, 6291725, 5600028 and 5496786). The active components of the high carbon polyol hydrocracking catalyst are mostly expensive metals such as platinum, palladium, ruthenium and nickel. In order to reduce the cost and increase the activity, the catalyst is usually prepared by a supported method, and the carrier is diatomaceous earth, activated carbon, alumina, Silica, a - A1 ₂ 0 ₃ , Ti0 ₂ (rutile), Zr0 ₂ (monoclinic phase), and the like. In order to overcome the hydrogen bonding in the reaction system and the acid by-products generated during the neutralization cracking, the sorbitol hydrocracking reaction is usually carried out under alkaline conditions in an aqueous phase.

Conradin (US3030429) reports that a sufficient base is added as a promoter in the polyol hydrocracking reaction system, the pH of the system is 11-12. 5, and the conversion rate of sorbitol is over 80%.

Sirkar (US4338472) also found that the base in the reaction system prevents the loss of the active component on the carrier. However, commonly used carriers such as alumina and silica are amphoteric compounds, which are difficult to stabilize for a long period of time under alkaline conditions, the catalyst carrier has a short life span, and the active component is liable to fall off and aggregate.

Elliott (Pub. No. US2002/0169344) reports on activated carbon, α - A1 ₂ 0 ₃ , Ti0 ₂ (gold Redstone) and Zr0 ₂ (monoclinic phase) are carriers and have high hydrothermal stability and alkali resistance under the reaction conditions. However, the activated carbon carrying metal is easily methanated under high pressure hydrogen and high temperature, which restricts the long-term effectiveness of activated carbon as a carrier; while α - Α1Λ, Ti0 ₂ (rutile), Zr0 ₂ (monoclinic crystal) as a carrier has a small surface area. The catalyst activity is difficult to increase, and Ti0 ₂ (rutile) is difficult to form and the price is high. Conventional metal catalysts based on commonly used carriers such as alumina and silica are easily corroded and dissolved under aqueous alkaline conditions, affecting the strength and life of the catalyst, the active components are easy to fall off and aggregate, and the pH of the system is Strict control requirements have constrained the large-scale industrial application of such catalysts. Therefore, how to solve the problem of catalyst alkali resistance is one of the main obstacles to the industrial application of such catalysts. The Raney-type catalyst prepared by the smelting method directly forms a metal skeleton structure, and has a developed honeycomb structure by using aluminum extraction activation treatment, and the specific surface is as high as 100 m 7 g. The Raney-type catalyst has good activity and high mechanical strength. It is not only used for hydrogenation and dehydrogenation of various unsaturated hydrocarbons, but also a good catalyst for some conversion processes such as dehalogenation and desulfurization. It is also widely used in the production of sugar liquid aqueous phase hydrogenation sugar alcohol, hydrogen peroxide and ethylene diamine. It has good hydrothermal stability and alkali resistance. The invention discloses a metal skeleton catalyst prepared by an ironing method and the application of the catalyst in high carbon alcohol hydrocracking, the catalyst has good activity and selectivity for high carbon alcohol hydrocracking, and is alkaline. It has high physical stability and chemical stability in aqueous solution. Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst for producing a high-carbon alcohol hydrocracking having a metal skeleton and a method for producing the catalyst, which has a simple preparation process and good repeatability. The catalyst produced by the method of the present invention has good activity, selectivity and stability for high carbon alcohol addition and cracking reaction, and has high physical stability and chemical stability especially in an alkaline aqueous solution. The catalyst of the present invention is prepared by a smelting method, and the obtained catalyst has a metal skeleton, does not require a carrier, and has high stability in a high-temperature alkaline aqueous solution, and is particularly suitable for hydrocracking of a high-carbon polyol. Specifically, the preparation method of the catalyst of the present invention comprises the following steps:

(1) nickel, cobalt and/or copper (hereinafter referred to as the first component) and one or more alkali-soluble amphoteric or non-metallic elements selected from the group consisting of aluminum, zinc, chromium, ruthenium, silicon, and the like (hereinafter referred to as the second group) a melting point to form an alloy at a temperature outside the use temperature; wherein the weight ratio of nickel, cobalt and/or copper to the alkali-soluble amphoteric element is 1:5 to 1:1, preferably the weight of both The ratio is 40:60~70:30, more preferably the weight ratio of the two is 45:55 65:35; the "far above the use temperature" means about 800-ΙΟΟΟΌ above the use temperature;

(2) one or more other metal or non-metal elements (hereinafter referred to as the third component) selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium,铑, silver, tungsten, ruthenium, osmium, platinum, gold, boron, phosphorus, selenium, tin, antimony, bismuth, antimony, etc. as cocatalyst components and alloyed with the above components, the above nickel, cobalt and/or copper metal The weight ratio to the third component element is 100: 0.1 to 200, preferably 100: 0 · 5 to 100;

(3) Dissolving all or part of the amphoteric element in the alloy with an alkali solution such as a sodium hydroxide solution; and obtaining a catalyst having a metal skeleton of the third group of elements as a promoter. Alternatively, in the method of the present invention, the order of the steps (2) and (3) may be reversed, that is, the catalyst of the present invention may also be prepared by the following method:

(1) nickel, cobalt and/or copper with one or more alkali-soluble amphoteric or non-metallic elements selected from the group consisting of aluminum, zinc, lanthanum, cerium, silicon, etc. (hereinafter referred to as the second group of elements) Melting at a temperature far higher than the use temperature to form an alloy; wherein the weight ratio of nickel, cobalt and/or copper to the amphoteric element is 1: 5 to 1:1, preferably the weight ratio of the two is 40: 60 to 70 : 30, more preferably the weight ratio of the two is 45:55-65:35; the "far above the use temperature" means about 800-1000 ° C above the use temperature; (2) with an alkaline solution, such as hydrogen Dissolving all or part of the amphoteric element in the alloy by a sodium oxide solution; (3) immersing the obtained catalyst semi-finished product in a solution of an acid or a salt of one or more of the following metals: vanadium, chromium, manganese, iron , cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, tungsten, niobium, selenium, tin, antimony and bismuth, etc., get a catalyst with a metal skeleton using such elements as a promoter, among which nickel, cobalt and/or Or the weight ratio of copper to the other elements as the cocatalyst is from 100:0.1 to 200, preferably from 100:0.5 to 100. Alternatively, in the method of the present invention, the steps (1) and (2) may be carried out in combination, that is, the nickel is smelted together with the metal or non-metal elements of the second and third components into an alloy by a melting method, and then the alkali is used. The solution dissolves all or part of the amphoteric metal in the alloy. Alternatively, step (3) as described in the method of the invention can be accomplished prior to use. Specifically, the method for producing a catalyst of the present invention is, for example: placing the two sexes in a crucible Metal or non-metal element, preferably aluminum, heated and melted in an electric furnace, adding nickel, cobalt and/or copper and other elements as cocatalyst at around 600-1200 ° C; stirring with a graphite rod for 20 - 30 minutes, then Pour out, cool, crush, ball mill, alloy nickel catalyst; use aluminum to remove aluminum before use. The other metal or non-metal element as the cocatalyst is one or more elements selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, Tungsten, ruthenium, rhodium, platinum, gold, boron, phosphorus, selenium, tin, antimony, bismuth and antimony; wherein the weight ratio of the first component to the second component is 1: 5 to 1: 1, preferably 40 5〜100。 The weight ratio of the first component to the third component is 100: 0. 1~200, preferably 100: 0. 5~100. Another alternative technical solution of the present invention is that no other metal is added in the above melting method, but the porous nickel catalyst is obtained by removing the amphoteric element by alkali dissolution (actually, porous nickel, cobalt and/or copper are obtained. Catalyst, for convenience of description, the "porous nickel, cobalt and/or copper catalyst" of the present invention is simply referred to as "nickel catalyst" or "nickel porous catalyst" herein, and then introduced into the catalyst by impregnation method selected from the following One or more metal or non-metal elements: vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, tungsten, niobium, selenium, tin, antimony and tellurium, etc. The catalyst is immersed in the acid or salt solution of the auxiliary agent to obtain a metal skeleton containing nickel, cobalt and

/ or copper and the porous nickel catalyst of the other metal or non-metal element. In the method for producing a catalyst of the present invention, the base to be used may be a hydride, an oxide or a hydroxide of an alkali metal or an alkaline earth metal, preferably a hydroxide such as sodium hydroxide or potassium hydroxide. One of the advantages of the method for producing a catalyst of the present invention is that, after the above treatment, the density of the catalyst is lowered, and the specific surface area is increased to 70 to 100 m ² , thereby increasing the activity of the catalyst. The second advantage of the method for producing a catalyst of the present invention is that the preparation process is simple and the repeatability is good due to the use of the melting method. It has high strength and thermal stability due to smelting preparation at temperatures well above the service temperature. The third advantage of the method for producing a catalyst of the present invention is that after the alloy is formed by the melt method, the amphoteric element in the alloy is dissolved by an alkali solution method before use, so that the active component nickel, cobalt and/or copper directly forms a porous catalyst. The structure allows the catalyst to have high physical and chemical stability under alkaline conditions. Another object of the present invention is to provide a catalyst for producing high carbon alcohol hydrocracking, which The catalyst is prepared by the above production method of the present invention and is a porous nickel catalyst having a metal skeleton, which is a novel catalyst with long life, high activity and high selectivity, and chemically stable under alkaline conditions under aqueous conditions under reaction conditions. Catalysts for physical and physical stability, such as catalysts with good stability to water, heat and alkali. The catalyst of the present invention comprises the following three components: the first component is nickel, cobalt and/or copper; and the second component is one or more amphoteric metal or non-metal elements selected from the group consisting of: aluminum , zinc, chromium, lanthanum and silicon, preferably aluminum; the third component is one or more other metal or non-metal elements selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, copper, zirconium , molybdenum, niobium, tantalum, silver, tungsten, niobium, tantalum, platinum, gold, boron, phosphorus, selenium, tin, antimony, bismuth and antimony. Their original weight ratios are: First component: second component = 1 : 5 to 1 : 1, preferably 40 : 60 to 70 : 30, more preferably 45: 55 to 65: 35; first component: third component = 100 : 0. 1 to 200, preferably 100 : 0 5~: 100. The catalyst has a metal skeleton formed of a first component and a second component, which is produced by the above-described method for producing a catalyst of the present invention. The first component of the catalyst of the invention is preferably metallic nickel; the second component is preferably aluminum; the third component is preferably selected from one or more of the following elements: titanium, chromium, manganese, cobalt, copper, zirconium, molybdenum , yttrium, lanthanum, silver, tungsten, lanthanum, boron, phosphorus, selenium, tin, antimony, bismuth and antimony; more preferably one or more of the following elements: cobalt, copper, molybdenum, niobium, tantalum, niobium, boron, phosphorus , tin, enamel and enamel. If desired, the catalyst of the present invention can be further loaded with modifications on its nickel porous catalyst to improve the selectivity of the catalyst. For example, the nickel porous catalyst is immersed in the following one or more metals at room temperature: vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, tungsten, niobium, selenium, tin, antimony Among the acid or salt solutions such as hydrazine, the immersion time is 24-48 hours, and the acid or salt concentration may be 1-20%. The catalyst of the present invention is a porous catalyst having a metal skeleton, and its preferred composition is: Ni-Al Sb, Ni-Al-Ru, Ni-Al-Mo, Ni-Al-Ce, Ni-Al-La, Ni- Al-B> Ni-Al-P, Ni-Al-Sn, Ni-Al-Re, Ni-Al-Co- Mo, Ni-Al-Cu-Mo, Ni-Al-Cu-Cr, Ni-Al- Cu-Ru, Ni-Al-Cu-Fe, Ni-Al-Sb-Cr, Ni-Al-Sn-Ru, and the like. The catalyst is a long-life new catalyst with high activity and high selectivity, and has chemical stability and physical stability under alkaline conditions under aqueous conditions, such as water, heat and alkali. Stability. Another object of the invention is to provide the use of the catalyst of the invention. The catalyst of the invention can For the hydrocracking of high carbon polyols, the low carbon polyol can be prepared by hydrocracking a high carbon polyol using the catalyst of the present invention. Accordingly, it is another object of the present invention to provide a process for preparing a low carbon polyol by hydrocracking a high carbon polyol using the catalyst of the present invention, and is particularly suitable for the addition of sorbitol prepared from renewable raw materials such as corn. Hydrogen cracking. The hydrocracking process of the high carbon polyol can employ a known method, characterized in that the catalyst disclosed in the present invention is used in the process. The hydrocracking process of the present invention comprises hydrocracking a high carbon polyol in the presence of a catalyst of the present invention under alkaline conditions at a high temperature and a high pressure in an aqueous phase to obtain a mixture of a plurality of low carbon polyols. , that is, a mixture of a C ₂₄ diol and a polyhydric alcohol, which can be purified by refining to obtain a certain proportion of a multi-component low-carbon polyol, or a single-component low-carbon polyol of a certain purity. The high carbon alcohol hydrocracking process of the present invention is characterized in that the process employs the catalyst of the present invention. The catalyst of the present invention comprises the following three components: the first component is nickel, cobalt and/or copper; and the second component is an amphoteric metal or non-metal selected from the group consisting of aluminum, zinc, chromium, ruthenium, silicon and the like. Element, preferably aluminum; the third component is one or more other metal or non-metal elements selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver , tungsten, rhodium, ruthenium, platinum, gold, boron, phosphorus, selenium, tin, antimony, bismuth and antimony, their original weight ratio is: First component: second component == 1 : 5~1 : 5〜100。 Preferably, the first component: the third component = 100: 0. 1~200, preferably 100: 0. 5~100. The catalyst has a metal skeleton formed of a first component and a second component, which is produced by the above-described method for producing a catalyst of the present invention. The catalyst of the present invention is a porous catalyst having a metal skeleton, and its preferred composition is: MAb Sb, Ni-Al-Ru, Ni-Al-Mo, Ni-Al-Ce, Ni-Al-La, Ni-Al -B, Ni-Al-P, Ni-Al-Sn, Ni-Al-Re, Ni-Al-Co-Mo, Ni-Al-Cu-Mo, Ni-A Cu-Cr, Ni-Al-Cu- Ru, Ni-A, Cu-Fe, Ni-Al-Sb-Cr, Ni-Al-Sn-Ru, and the like. The catalyst is a long-life new catalyst with high activity and high selectivity, and has chemical stability and physical stability under alkaline conditions under aqueous conditions, such as water, heat and alkali. Stability. If desired, the catalyst of the present invention may further be modified on its nickel porous structure, Thereby improving the selectivity of the catalyst. For example, the nickel porous catalyst is immersed in the following one or more metals at room temperature: vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, tungsten, niobium, selenium, tin, antimony Among the acid or salt solutions such as hydrazine, the immersion time is 24-48 hours, and the acid or salt concentration may be 1-20%. In the above hydrocracking process, the weight ratio of the catalyst of the present invention to the reaction liquid is from 2:98 to 20:80. In the above hydrocracking process, the basic conditions can be achieved by adding a basic compound such as sodium hydroxide, potassium hydroxide or the like, preferably using sodium hydroxide. In the above hydrocracking method, the weight ratio of the high carbon polyol to water is a high carbon polyol aqueous solution concentration of 5 to 70% by weight, preferably about 25 to 60% by weight; the molar ratio of the high carbon polyol to the sodium hydroxide It is 5-15:1, preferably 6-10:1. The conditions of the hydrocracking reaction are: a reaction temperature of 190 to 280 ° C, preferably 230 to 250 ° C, and a reaction pressure of 7 to 15 MPa, preferably 10 to 12 MPa. A method for producing a low carbon polyol and a multicomponent low carbon polyol by aqueous phase hydrocracking of a high carbon polyol according to the present invention, the basic weight composition of a low carbon polyol mixture obtained by hydrocracking sorbitol Usually: ethylene glycol 5-30%; propylene glycol 15-60%; glycerol 5- 20%; various butanediol isomers 1-12%, wherein: 1, 2-butanediol 0. 5 -6%, 1, 4-butanediol 0. 5-6% and 2,3-butanediol 0. 5-6%; the remainder is a by-product fraction, accounting for about 3-16%, including methanol. 0. 75-1. 5%, ethanol is about 0. 75- 1. 5%, unreacted sorbitol is about 0.2%, organic acid salt is about 1-5%, methane, carbon dioxide, etc. is about 1. -5%. Preferably, the basic weight composition of the low carbon polyol mixture prepared by the method is: ethylene glycol 15-30%; propylene glycol 30-60%; glycerol 15- 30; various butanediol isomers 5 - 12%, of which: 1, 2-butanediol 3-6%, 1, 4-butanediol 1-2% and 2, 3-butanediol 2-4%; the rest are by-product fractions 2 - 5%, The organic acid salt is about 2, 5%, the ethanol is about 0. 75- 1. 5%, the unreacted sorbitol is about 0.2-5%, the organic acid salt is about 2 -3%, a small amount of methane, and other substances are about 1 - 5%. The low carbon polyol mixture obtained by the process of the present invention by a conventional separation and refining process gives various single component low carbon polyols, or a desired low molecular weight mixed low carbon polyol. These low-carbon polyols or low-carbon polyol mixtures with a certain composition can be used for polyester materials, antifreeze, Lubricants, plasticizers, surfactants, etc. The method for producing a catalyst of the invention adopts a melting method, and the preparation process is simple and the repeatability is good. It has high strength and thermal stability due to smelting preparation at temperatures well above the service temperature. The catalyst produced by the method has a metal skeleton structure, high specific surface area, good activity and selectivity for cracking of high carbon polyol, and high physical stability and chemical stability under alkaline conditions of aqueous phase. The catalyst of the invention is particularly suitable for the hydrocracking process of sorbitol, and the catalyst of the invention can overcome various problems that the conventional catalyst is difficult to be stable for a long period under alkaline conditions, the catalyst carrier has a short life span, and the active component is easy to fall off and aggregate. detailed description

The materials and methods of the present invention are described in detail below with reference to the accompanying drawings. However, these examples do not limit the scope of the invention in any way. Example 1

1. Preparation of catalyst 1:

Put 100g of metal aluminum in the crucible, heat and melt it in an electric furnace, add 98g of metallic nickel and 2g of metal crucible at about 1000 °C, stir with a graphite rod at 1200-1300 ° C for 20-30 minutes, then pour out, Cooling, crushing, ball milling, and catalyst A. The aluminum was removed by alkali dissolution before use, and 1.5 L of 20% sodium hydroxide was added to 500 g of the catalyst, kept at 80 ° C for 2 hours, and then washed with deionized water to pH = 7.5.

2. Catalyst 1 is used for sorbitol hydrocracking reaction

24 g of catalyst A, 300 ml of 25% sorbitol, and 2 g of sodium hydroxide were placed in a 500 ml autoclave, and after replacing with nitrogen and hydrogen in this order, the temperature was raised to 200 ° C, and the hydrogen pressure was maintained at 12 MPa. After 7 hours of reaction, the concentration of each component of the obtained product in the system was: sorbitol concentration 3.74%, ethylene glycol concentration 1.82%, propylene glycol concentration 4.15%, 1,4-butanediol concentration 0.08%, 1,2- The concentration of butanediol was 0.59%, the concentration of methanol was 0.06%, the concentration of ethanol was 0.33%, the concentration of propanol was 0%, the concentration of formic acid was 1.07%, the concentration of acetic acid was 2.03%, and the concentration of lactic acid was 1.02%.

Example 2

1. Preparation of Catalyst 2:

Catalyst 2 was prepared in the same manner as in Example 1, and the metal added was 100 g of metal aluminum, 80 g. Metal nickel, 19g metal copper and lg metal iron.

2. Catalyst 2 is used for sorbitol hydrocracking reaction

15 g of the catalyst 2, 300 ml of 25% sorbitol, and 3 g of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and the temperature was raised to 220 ° C to maintain a hydrogen pressure of 12 MPa. After 9 hours of reaction, the concentration of each component of the obtained product in the system was: sorbitol concentration 0.15%, ethylene glycol concentration 2.57%, propylene glycol concentration 8.20%, 1,4-butanediol concentration 0.25%, 1,2- The concentration of butanediol was 0.87%, the concentration of methanol was 0.33%, the concentration of ethanol was 0.43%, the concentration of propanol was 0.09%, the concentration of formic acid was 0.97%, the concentration of acetic acid was 1.98%, and the concentration of lactic acid was 0.87%.

Example 3

1. Preparation of catalyst 3:

The catalyst 3 was prepared in the same manner as in Example 1. The metal to be added was 100 g of metallic aluminum, 90 g of metallic nickel, and 10 g of metallic tin, respectively.

2. Catalyst 3 is used for sorbitol hydrocracking reaction

30 _{g of} catalyst 3, 300 ml of 25% sorbitol, and lg of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and the temperature was raised to 215 ° C to maintain a hydrogen pressure of 10 MPa. After 10 hours of reaction, the concentration of each component of the obtained product in the system was: sorbitol concentration 2.73%, ethylene glycol concentration 2.84%, propylene glycol concentration 7.80%, 1,4-butanediol concentration 0.17%, 1,2- The concentration of butanediol was 0.85%, the methanol concentration was 0.27%, the ethanol concentration was 0.21%, the propanol concentration was 0.05%, the formic acid concentration was 1.12%, the acetic acid concentration was 2.05%, and the lactic acid concentration was 1.30%.

Example 4

1. Preparation of catalyst 4:

The catalyst 4 was prepared in the same manner as in Example 1. The metal to be added was 100 g of aluminum metal, 92 g of metallic nickel, 7 g of metallic tin and lg of metallic ruthenium, respectively.

2. Catalyst 4 is used for sorbitol hydrocracking reaction

After 18g of the catalyst 4, 300ml 25% sorbitol, 2g sodium hydroxide was placed in a 500ml autoclave, successively substituted with nitrogen and hydrogen, heated to 210 ° C, maintaining the hydrogen pressure is 12Mpa ₀ 6 hours of reaction, the resulting product The concentration of each component in the system is: sorbitol concentration 1.33 %, ethylene glycol concentration 1.84%, propylene glycol concentration 8.78%, 1,4-butanediol concentration 0.12%, 1,2-butanediol concentration 0.78%, Methanol concentration 0.31%, ethanol concentration 0.27%, propanol concentration 0.07%, formic acid concentration 0.85%, acetic acid concentration 1.97%, and lactic acid concentration 0.93%. Example 5

1. Preparation of catalyst 5:

The catalyst 5 was prepared in the same manner as in Example 1. The metal to be added was 100 g of metal aluminum, 95 g of metal nickel, 4 g of metal copper and lg of metal ruthenium, respectively.

2. Catalyst 5 is used for sorbitol hydrocracking reaction

(1) 18 g of catalyst 5, 300 ml of 25% sorbitol, 2 g of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and then the temperature was raised to 225 ° C, and the hydrogen pressure was maintained at l lMpao for 16 hours. The concentration of each component of the obtained product in the system is: sorbitol concentration 0.91%, ethylene glycol concentration 2.79%, propylene glycol concentration 8.40%, 1,4-butanediol concentration 0.23%, 1,2-butanediol concentration 0.88%, methanol concentration 0.39%, ethanol concentration 0.22%, propanol concentration 0.07%, formic acid concentration 1.21%, acetic acid concentration 2.32%, and lactic acid concentration 0.87%.

(2) 25 g of catalyst 4, 300 ml of 40% sorbitol, 3.2 g of sodium hydroxide were placed in a 500 ml autoclave, and after replacing with nitrogen and hydrogen in sequence, the temperature was raised to 220 ° C, and the hydrogen pressure was maintained at 12 MPa. After 10 hours of reaction, the concentration of each component of the obtained product in the system was: sorbitol concentration 5.22%, ethylene glycol concentration 5.03%, propylene glycol concentration 8.35 %, 1,4-butanediol concentration 0.32%, 1,2- The concentration of butanediol was 2.09%, the methanol concentration was 0.54%, the ethanol concentration was 0.44%, the propanol concentration was 0.09%, the formic acid concentration was 1.89%, the acetic acid concentration was 3.98%, and the lactic acid concentration was 3.09%. Example 6

1. Preparation of catalyst 6:

The catalyst 6 was prepared in the same manner as in Example 1. The metal to be added was 100 g of metal aluminum, 95 g of metal nickel, and 5 g of metal ruthenium, respectively.

2. Catalyst 6 is used for sorbitol hydrocracking reaction

(1) 18 g of a catalyst 5, 300 ml of 25% sorbitol, and 2 g of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and the temperature was raised to 225 ° C to maintain a hydrogen pressure of 13 MPa. After 8 hours of reaction, the concentration of each component of the obtained product in the system was: sorbitol concentration 3.12%, ethylene glycol concentration 2.91%, propylene glycol concentration 7.57%, 1,4-butanediol concentration 0.22%, 1,2- The concentration of butanediol was 0.67%, the concentration of methanol was 0.32%, the concentration of ethanol was 0.26%, the concentration of propanol was 0.43%, the concentration of formic acid was 1.09%, the concentration of acetic acid was 1.97%, and the concentration of lactic acid was 0.46%. (2) 30 g of catalyst 5, 300ml 60% of sorbitol, 4.8 g of sodium hydroxide was placed in a 500 ml autoclave, successively substituted with nitrogen and hydrogen, heated to 220 ° C, holding the reaction hydrogen pressure is 12MPa ₀ At 8 hours, the concentration of each component in the system was: sorbitol concentration 12.56%, ethylene glycol concentration 7.73%, propylene glycol concentration 13.02%, 1,4-butanediol concentration 0.64%, 1,2-butyl The diol concentration was 3.40%, the methanol concentration was 0.86%, the ethanol concentration was 0.85%, the propanol concentration was 0.14%, the formic acid concentration was 3.45%, the acetic acid concentration was 4.68%, and the lactic acid concentration was 5.99%.

Example 7

1. Preparation of catalyst 7:

The catalyst 7 was prepared in the same manner as in Example 1. The metal to be added was 100 g of metallic aluminum, 55 g of metallic nickel, 43 g of metallic cobalt and 2 g of metallic molybdenum, respectively.

2. Catalyst 7 is used for sorbitol hydrocracking reaction

16 g of catalyst 7, 300 ml of 25% sorbitol, lg of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and the temperature was raised to 215 ° C, and the hydrogen pressure was maintained at 1 OMpao for 3 hours. The concentration of each component in the system is: sorbitol concentration 0.62%, ethylene glycol concentration 2.14%, propylene glycol concentration 5.78%, 1,4-butanediol concentration 0.30%,

1,2-butanediol concentration 0.44%, methanol concentration 0.42%, ethanol concentration 0.64%, propanol concentration 0.08%, formic acid concentration 1.02%, acetic acid concentration 1.56%, and lactic acid concentration 0.76%.

Example 8

1. Preparation of Catalyst 8:

The catalyst 8 was prepared in the same manner as in Example 1. The metal to be added was 100 g of metal aluminum, 95 g of metal nickel, and 5 g of boron, respectively.

2. Catalyst 8 is used for sorbitol hydrocracking reaction

20 g of catalyst 8, 300 ml of 25% sorbitol, and 2 g of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and then the temperature was raised to 230 ° C, and the hydrogen pressure was maintained at lOMpao for 9 hours. The concentration of the components in the system is: sorbitol concentration

1.07%, ethylene glycol concentration 3.09%, propylene glycol concentration 7.79%, 1,4-butanediol concentration 0.45%, 1,2-butanediol concentration 0.97%, methanol concentration 0.46%, ethanol concentration 0.32%, propanol concentration 0.04%, formic acid concentration 1.67%, acetic acid concentration 2.45%, and lactic acid concentration 0.79%.

Example 9 1. Preparation of Catalyst 9:

The catalyst 9 was prepared in the same manner as in Example 1. The metal to be added was 100 g of aluminum metal, 97 g of metallic nickel, and 3 g of phosphorus, respectively.

2. Catalyst 9 is used for sorbitol hydrocracking reaction

26 g of catalyst 9, 300 ml of 25% sorbitol, and lg of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and the temperature was raised to 215 Torr, and the hydrogen pressure was maintained at lOMpao for 7 hours. The concentrations in the system are: sorbitol concentration 0.24%, ethylene glycol concentration 2.73%, propylene glycol concentration 6.96%, 1,4-butanediol concentration 0.35%, 1,2-butanediol concentration 0.78%, methanol concentration 0.47%, ethanol concentration 0.29%, propanol concentration 0.12%, formic acid concentration 1.28%, acetic acid concentration 2.67%, and lactic acid concentration 0.97%. Example 10

1. Preparation of catalyst 10:

The catalyst 10 was prepared in the same manner as in Example 1. The metal to be added was 100 g of aluminum metal, 98 g of metallic nickel, and 2 g of molybdenum, respectively.

2. Catalyst 10 is used for sorbitol hydrocracking reaction

14 g of catalyst 10, 300 ml of 25% sorbitol, 2 g of sodium hydroxide were placed in a 500 ml autoclave, followed by replacement with nitrogen and hydrogen, and then the temperature was raised to 200 ° C, and the hydrogen pressure was maintained at lOMpao for 3 hours. The concentration of the components in the system is: sorbitol concentration 1.03%, ethylene glycol concentration 1.45%, propylene glycol concentration 3.09%, 1,4-butanediol concentration 0.23%, 1,2-butanediol concentration 0.61%, methanol The concentration was 0.36%, the ethanol concentration was 0.19%, the propanol concentration was 0.02%, the formic acid concentration was 1.98%, the acetic acid concentration was 2.67%, and the lactic acid concentration was 0.87%. Example 11

1. Preparation of catalyst 11:

Put 100g of metal aluminum in the crucible, heat and melt it in an electric furnace, add 100g of metallic nickel at about 1000 °C, stir with a graphite rod at 1200-1300 °C for 20-30 minutes, then pour, cool, crush, Ball milling, the catalyst G. The aluminum was removed by alkali dissolution before use, and 1.5 L of 20% sodium hydroxide was added to 500 g of the catalyst, kept at 80 ° C for 2 hours, and then washed with deionized water to pH = 7.5. The catalyst was impregnated with a 10% strength citric acid solution at room temperature for 48 hours.

2. Catalyst 11 is used for sorbitol hydrocracking reaction 27 g of catalyst 11, 300 ml 25 ° /. The sorbitol, 3 g of sodium hydroxide was placed in a 500 ml autoclave, replaced with nitrogen and hydrogen in that order, and then heated to 230 ° C to maintain a hydrogen pressure of 12 MPa. The concentration of the components of the obtained product in the system is: sorbitol concentration 1.79%, ethylene glycol concentration 2.84%, propylene glycol concentration 8.09%, 1, 4-butanediol concentration 0 15%。 The concentration of the ethanol is 0.98%, the concentration of the ethanol is 0.29%, the concentration of the propanol is 0. 11%, the concentration of the formic acid is 0.97%, and the concentration of the acetic acid is 1. 09%, lactic acid concentration 2.07%. The catalyst formulation for the hydrogenation of high carbon alcohol of the invention can form a stable alloy structure during the smelting process, and the surface area of the catalyst can reach 70-100 m ² after the aluminum activation. The catalyst is used for hydrocracking of high carbon alcohols, has good low carbon polyol selectivity, and the metal alloy has better stability in the high temperature alkaline aqueous solution of the reaction system than other commonly used catalysts, and is particularly suitable. Industrialized production of large-scale high-carbon alcohol hydrocracking. The embodiments of the present invention have been described in detail, and it is obvious to those skilled in the art that many modifications and changes can be made without departing from the spirit of the invention. Inside.

Claims

The claims are:

What is claimed is: 1. A method of preparing a catalyst having a metal skeleton, the method comprising the steps of:

(1) nickel, cobalt and/or copper (hereinafter referred to as the first component) and one or more alkali-soluble amphoteric or non-metallic elements selected from the group consisting of aluminum, zinc, chromium, cerium and silicon ( Hereinafter referred to as the second component), it is smelted at a temperature far higher than the use temperature to form an alloy; wherein the weight ratio of nickel, cobalt and/or copper and alkali-soluble amphoteric elements is 1:5 to 1:1. ;

(2) one or more other metal or non-metal elements (hereinafter referred to as the third component) selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, Anthracene, silver, tungsten, ruthenium, osmium, platinum, gold, boron, rock, selenium, tin, antimony, bismuth, antimony, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony, bismuth, antimony The weight ratio of such elements is 100:0.1~

200; and

(3) dissolving all or part of the amphoteric elements in the alloy with an alkali solution;

A catalyst having a metal skeleton with a third component element as a promoter is obtained.

A method of producing a metal skeleton catalyst according to claim 1, wherein said amphoteric element is preferably aluminum.

A method of producing a metal skeleton catalyst according to claim 1, wherein the order of said steps (2) and (3) can be reversed.

A method of producing a metal skeleton catalyst according to claim 1, wherein said steps (1) and (2) are carried out in combination.

5. A method of preparing a metal skeleton catalyst according to claim 1, wherein said step (3) can be carried out before use.

6. A method of preparing a metal skeleton catalyst according to any one of claims 1 to 5, wherein said third component is selected from one or more of the following elements: titanium, chromium, manganese, cobalt, copper, zirconium , molybdenum, niobium, tantalum, niobium, tungsten, niobium, boron, phosphorus, selenium, tin, antimony, bismuth and antimony; preferably one or more of the following elements: cobalt, copper, molybdenum, niobium, tantalum, niobium, boron, Phosphorus, tin, antimony and bismuth.

7. A method of preparing a metal skeleton catalyst according to claim 6, wherein the weight ratio of said first component to said second component is from 40:60 to 70:30, preferably from 45:55 to 65:35.

8. A method of preparing a metal skeleton catalyst according to claim 7, wherein said method comprises placing an element of the second component in a crucible, heating and melting in an electric furnace, and adding the first component at about 600 to 120 (about TC). And the third component as a cocatalyst, stirred with a graphite rod, then decanted, cooled, crushed, and ball milled to form an alloy nickel catalyst, and the element of the second component is removed by alkali dissolution before use.

9. A metal skeleton catalyst prepared by the process according to any one of claims 1-8, said catalyst comprising the following three components: the first component is nickel, cobalt and/or copper; the second component is One or more other metal or non-metal elements selected from the group consisting of aluminum, zinc, chromium, ruthenium and silicon; and the third component is one or more other metal or non-metal elements selected from the group consisting of: titanium , vanadium, chromium, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, tungsten, niobium, tantalum, platinum, gold, boron, phosphorus, selenium, tin, antimony, bismuth and antimony, their original The weight ratio is: first component: second component = 1: 5~1: 1; first component: third component = 100: 0. 1-200; the catalyst has the first component and The metal skeleton formed by the second component.

10. The metal skeleton catalyst according to claim 9, wherein the weight ratio of each component is preferably: the weight ratio of the first component to the second component is 40: 60 to 70: 30, more preferably 45: 55~ 65至35。 The weight ratio of the first component to the third component is preferably 100: 0. 5-100.

11. A metal skeleton catalyst according to claim 10, wherein the preferred composition of each component is: Ni-A; L-Sb, Ni-Al-Ru, Ni-Al-Mo, Ni-Al Ce, Ni-A ] ~ La, Ni- AB, Ni-Al-P, Ni- A: i-Sn, Ni-Al- Re, Ni-Al-Co-Mo^ Ni-Al-Cu- Mo, Ni-Al Cu-Cr Ni-Al-Cu-Ru, Ni-Al-Cu-Fe, Ni-Al-Sb-Cr or Ni-Ab Sn-Ru.

The metal skeleton catalyst according to any one of claims 9 to 11, wherein the catalyst is further load-modified, and the preferred modification method is to immerse the nickel porous catalyst in one or more of the following metals at room temperature. : In an acid or salt solution of vanadium, complex, manganese, iron, cobalt, copper, zirconium, molybdenum, niobium, tantalum, silver, tungsten, niobium, selenium, tin, antimony and bismuth, the immersion time is 24-48 hours. The concentration of the acid or salt may be from 1 to 20%.

13. Use of a metal framework catalyst according to any of claims 9-12 in a process for the hydrocracking of a high carbon polyol to produce a low carbon polyol.

14. A process for hydrocracking a high carbon polyol to produce a low carbon polyol, the method comprising subjecting a high carbon polyol to a hydrocracking reaction in an aqueous phase under high temperature and high pressure under alkaline conditions. a mixture of ₂₄ diol and polyol, purified by refining, to obtain a certain proportion of multi-component low-carbon polyol, or a single-component low-carbon polyol of a certain purity; characterized in that the hydrocracking is It is carried out in the presence of a catalyst according to any one of claims 9-12.

A process for the preparation of a low carbon polyol by hydrocracking according to claim 14, wherein said high carbon polyol is sorbitol, preferably said sorbitol is prepared from corn raw material.

A process for producing a low carbon polyol by hydrocracking according to claim 15, wherein the amount of the catalyst used, i.e., the weight ratio of the catalyst to the reaction liquid is from 2:98 to 20:80.

A process for producing a low carbon polyol by hydrocracking according to claim 15, wherein the concentration of the aqueous sorbitol solution is from 5 to 70% by weight; preferably, the concentration of the aqueous solution of sorbitol is preferably from 25 to 60% by weight.

18. A process for the preparation of a low carbon polyol by hydrocracking according to claim 15, wherein the molar ratio of sorbitol to sodium hydroxide is from 5 to 15:1; preferably from 6 to 10:1.

A process for producing a low carbon polyol by hydrocracking according to claim 15, wherein the reaction temperature is 190 to 280 ° C, and the reaction pressure is 7 to 15 MPa; preferably, the reaction temperature is preferably 230 to 250 ° C, The pressure is preferably 9-12 MPa.

20. A process for the preparation of a low carbon polyol by hydrocracking according to claim 15, wherein the basic weight composition of the low carbon polyol prepared by the process is: ethylene glycol 5-30%; propylene glycol 15-60% ; succinol 5-20%; various butanediol isomers 1-12%, wherein: 1, 2-butanediol 0. 5-6%, 1, 4-butanediol 0. 5- 6 % 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 1. 5%, unreacted sorbitol is about 0. 2-5%, organic acid salt is about 1-5%, methane, carbon dioxide, etc. is about 1-5%; preferably low carbon polyol prepared by the method The weight composition of the mixture is: ethylene glycol 15-30%; propylene glycol 30-60%; glycerol 15- 30; various butanediol isomers 5-12%, wherein: 1, 2-butanediol 3 - 6%, 1, 4-butanediol 1-2% and 2, 3-butanediol 2 - 4%; the remainder is a by-product fraction, accounting for about 3 - 16%, including methanol is about 0. 75- 1. 5%, ethanol is about 0. 75-1. 5%, unreacted sorbitol is about 0. 2-5%, organic acid salt is about 23.3%, small amount of methane, other substances The quality is about 1-5%.