CN113617345B - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113617345B CN113617345B CN202110933409.9A CN202110933409A CN113617345B CN 113617345 B CN113617345 B CN 113617345B CN 202110933409 A CN202110933409 A CN 202110933409A CN 113617345 B CN113617345 B CN 113617345B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- copper
- water
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst, a preparation method and application thereof. The catalyst can be used for preparing the hydroxyacetone by catalyzing the glycerol, and has the advantages of high selectivity, simple preparation, high yield of catalytic products, high purity and long service life.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a catalyst and a preparation method and application thereof.
Background
Along with the increasing shortage of energy sources, the biodiesel industry is rapidly developed, and a large amount of byproduct glycerol in the biodiesel production process is utilized to efficiently convert glycerol into high-added-value products, so that the economic benefit of the whole biodiesel industry, such as the preparation of hydroxyacetone and 1, 2-propanediol by utilizing glycerol, is improved.
One of the key cores in the preparation of hydroxyacetone from glycerol is the development of efficient catalysts. Chinese patent application CN109665952a discloses a catalyst for preparing hydroxyacetone from glycerol, which can use pure glycerol feed instead of glycerol solution feed and has high conversion rate of glycerol (more than 97%) and high hydroxyacetone selectivity (more than 95%) under reduced pressure reaction conditions. However, the catalyst takes copper chromite as an active component, chromium is toxic and easy to pollute the environment, and development of an efficient non-chromium catalyst for preparing hydroxyacetone is urgently needed.
Chinese patent application CN112090424A discloses a catalyst for preparing 1, 2-propylene glycol by hydrogenolysis of glycerol, which has good activity, selectivity and stability, but relatively harsh working conditions, the reaction pressure for catalyzing the hydrogenolysis of glycerol is 4-8 MPa, the pressure is too high, the requirements on equipment are high, and the operation danger coefficient is high.
The Cu-based catalyst has the defect that metal Cu is easy to agglomerate and grow up, so that the technical difficulty in developing efficient and stable glycerol for preparing hydroxyacetone is how to effectively stabilize Cu and prevent Cu from sintering and growing up.
Therefore, development of a catalyst for preparing hydroxyacetone by non-chromium with high catalytic speed, long service life, multiple times of repeated use, high reaction selectivity and high yield is needed.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst, a preparation method and application thereof.
In a first aspect, the present invention provides a catalyst.
The catalyst consists of a metal active component and an oxide carrier, wherein the metal active component is loaded on the oxide carrier, the metal active component is elemental copper, and the oxide carrier comprises at least two selected from lanthanum oxide, yttrium oxide, ytterbium oxide, aluminum oxide and zirconium dioxide.
In some embodiments, the oxide support comprises an oxide support I selected from at least one of lanthanum oxide, yttrium oxide, ytterbium oxide, and zirconium oxide, and aluminum oxide. In some embodiments, the oxide support comprises or is alumina and zirconia. In some embodiments, the oxide support is yttria and alumina. In some embodiments, the oxide support comprises or is lanthanum oxide and aluminum oxide. In some embodiments, the oxide support comprises or is ytterbium trioxide and aluminum trioxide.
In some embodiments, the oxide support comprises aluminum oxide and zirconium dioxide in a molar ratio of 0.2:1.0 to 0.6:1.0. In some embodiments, the oxide support comprises aluminum oxide and zirconium dioxide in a molar ratio of 0.3:1.0 to 0.5:1.0. In some embodiments, the oxide support comprises aluminum oxide and zirconium dioxide in a molar ratio of 0.4:1.0.
In some embodiments, the oxide support comprises an oxide support I selected from at least one of lanthanum oxide, yttrium oxide, and ytterbium oxide, and aluminum oxide. In some embodiments, the oxide support comprises an oxide support I and an aluminum oxide, the oxide support I being selected from at least one of lanthanum oxide, yttrium oxide, and ytterbium oxide, the molar ratio of the oxide support I to the aluminum oxide being from 0.5:1.0 to 2.0:1.0. In some embodiments, the oxide support comprises an oxide support I and an aluminum oxide, the oxide support I being selected from at least one of lanthanum oxide, yttrium oxide, and ytterbium oxide, the molar ratio of the oxide support I to the aluminum oxide being from 0.8:1.0 to 1.5:1.0. In some embodiments, the oxide support comprises an oxide support I and an aluminum oxide, the oxide support I being selected from at least one of lanthanum oxide, yttrium oxide, and ytterbium oxide, the molar ratio of the oxide support I to the aluminum oxide being from 0.8:1 to 1.0:1.0. In some embodiments, the oxide support comprises an oxide support I and an aluminum oxide, the oxide support I being selected from at least one of lanthanum oxide, yttrium oxide, and ytterbium oxide, the molar ratio of the oxide support I to the aluminum oxide being from 0.9:1.0 to 1.0:1.0. In some embodiments, the oxide support comprises an oxide support I and an aluminum oxide, the oxide support I being selected from at least one of lanthanum oxide, yttrium oxide, and ytterbium oxide, the molar ratio of the oxide support I to aluminum oxide being 0.94:1.0.
In some embodiments, the oxide support is yttrium oxide and aluminum oxide in a molar ratio of 0.5:1.0 to 2.0:1.0. In some embodiments, the oxide support is yttrium oxide and aluminum oxide in a molar ratio of 0.8:1.0 to 1.5:1.0. In some embodiments, the oxide support is yttrium oxide and aluminum oxide in a molar ratio of 0.8:1 to 1.0:1.0. In some embodiments, the oxide support is yttrium oxide and aluminum oxide in a molar ratio of 0.9:1.0 to 1.0:1.0. In some embodiments, the oxide support is yttria and alumina, and the molar ratio of yttria to alumina is 0.94:1.0.
In some embodiments, the oxide support comprises lanthanum oxide and aluminum oxide in a molar ratio of 0.5:1.0 to 2.0:1.0. In some embodiments, the oxide support comprises lanthanum oxide and aluminum oxide in a molar ratio of 0.8:1.0 to 1.5:1.0. In some embodiments, the oxide support comprises lanthanum oxide and aluminum oxide in a molar ratio of 0.8:1 to 1.0:1.0. In some embodiments, the oxide support comprises lanthanum oxide and aluminum oxide in a molar ratio of 0.9:1.0 to 1.0:1.0. In some embodiments, the oxide support comprises lanthanum oxide and aluminum oxide in a molar ratio of 0.94:1.0.
In some embodiments, the oxide support is ytterbium trioxide and aluminum trioxide in a molar ratio of 0.5:1.0 to 2.0:1.0. In some embodiments, the oxide support is ytterbium trioxide and aluminum trioxide in a molar ratio of 0.8:1.0 to 1.5:1.0. In some embodiments, the oxide support is ytterbium trioxide and aluminum trioxide in a molar ratio of 0.8:1 to 1.0:1.0. In some embodiments, the oxide support is ytterbium trioxide and aluminum trioxide in a molar ratio of 0.9:1.0 to 1.0:1.0. In some embodiments, the oxide support is ytterbium trioxide and aluminum trioxide in a molar ratio of 0.94:1.0.
The weight percentage of the metal active component can be 10-70% based on the total weight of the catalyst, and the balance is the oxide carrier. In some embodiments, the weight percent of the metal active component is preferably 15% -65% based on the total weight of the catalyst, with the balance being the oxidation support. In some embodiments, the weight percent of the metal active component is preferably 15% to 50% based on the total weight of the catalyst, with the balance being the oxidation support. In some embodiments, the weight percent of the metal active component is preferably 15% to 46% based on the total weight of the catalyst, with the balance being the oxidation support.
In some embodiments, the oxide support comprises at least one member selected from the group consisting of an oxide support I and an aluminum oxide, the oxide support I being selected from the group consisting of zirconium oxide, lanthanum oxide, yttrium oxide, and ytterbium oxide; based on the total weight of the catalyst, the weight percentage of the metal active component is 35-47%, and the balance is the oxidation carrier. In some embodiments, the oxide support comprises at least one member selected from the group consisting of an oxide support I and an aluminum oxide, the oxide support I being selected from the group consisting of zirconium oxide, lanthanum oxide, yttrium oxide, and ytterbium oxide; based on the total weight of the catalyst, the weight percentage of the metal active component is 35-47%, the weight percentage of the aluminum oxide is 13-18%, and the balance is the oxide carrier I. In some embodiments, the oxide support comprises a support selected from the group consisting of oxide support I and aluminum oxide, the oxide support I being selected from at least one of zirconium dioxide, lanthanum oxide, and ytterbium oxide; based on the total weight of the catalyst, the weight percentage of the metal active component is 35-40%, the weight percentage of the aluminum oxide is 13-16%, and the balance is the oxide carrier I. In some embodiments, the oxide support comprises a catalyst selected from the group consisting of an oxide support I and an aluminum oxide, the oxide support I being yttrium oxide; based on the total weight of the catalyst, the weight percentage of the metal active component is 45-47%, the weight percentage of the aluminum oxide is 15-18%, and the balance is the oxide carrier I.
The reason that the service life of the catalyst is not long is that simple substance copper is sintered and agglomerated in the using process, and the acid-base property of the oxide carrier adopted in the prior art is not suitable, so that the binding force between the carrier and copper is reduced, and further, the copper is easy to agglomerate, and the catalyst is deactivated. The catalyst provided by the invention adopts the oxide carrier with proper acidity and alkalinity as the carrier of the elemental copper, the oxide carrier has stronger binding force with the elemental copper than other oxide carriers, the elemental copper can be anchored, the agglomeration process of the metal copper is delayed, the service life of the catalyst is prolonged, and other carrier oxides such as chromite or alumina have strong acidity, have weaker binding force with the copper, are easy to agglomerate, lead to the deactivation of the catalyst and lead to the short service life of the catalyst. In addition, the simple substance copper and the oxide carrier can be used for catalyzing the glycerol in a synergistic way, so that the selectivity and the efficiency are high.
In a second aspect, the present invention provides a process for preparing the catalyst of the first aspect.
A method of preparing the catalyst of the first aspect, comprising the steps of: mixing a complexing agent, a protective agent and a reducing agent with a copper source aqueous solution, wherein the copper source aqueous solution is a copper salt-containing aqueous solution, performing a first reaction under the protection of inert gas, cooling, adding a precipitant-containing aqueous solution and an oxide carrier precursor salt-containing aqueous solution for aging, and performing aftertreatment to obtain the catalyst.
The complexing agent may include at least one selected from the group consisting of methylamine, ethylenediamine, sodium nitrilotriacetate, and disodium ethylene diamine tetraacetate.
The protective agent may include at least one selected from ethanol, ethylene glycol, and glycerol.
The reducing agent may include at least one selected from hydrazine hydrate, sodium borohydride, and potassium borohydride.
The inert gas may include at least one selected from nitrogen and argon.
The precipitant may include at least one selected from the group consisting of sodium hydroxide, urea, ammonia, ammonium bicarbonate, ammonium carbonate, sodium carbonate, and potassium carbonate.
The copper salt may be a water-soluble copper salt.
The water-soluble copper salt may include at least one selected from copper nitrate, copper sulfate, and copper chloride.
The oxide support precursor salt may include at least one selected from the group consisting of a water-soluble lanthanum salt, a water-soluble yttrium salt, a water-soluble ytterbium salt, a water-soluble aluminum salt, and a water-soluble zirconium salt. In some embodiments, the oxide support precursor salts include water-soluble lanthanum salts and water-soluble aluminum salts. In some embodiments, the oxide support precursor salts include water-soluble yttrium salts and water-soluble aluminum salts. In some embodiments, the oxide support precursor salts include water-soluble ytterbium salts and water-soluble aluminum salts. In some embodiments, the oxide support precursor salts include water-soluble zirconium salts and water-soluble aluminum salts.
The water-soluble lanthanum salt may include at least one selected from lanthanum nitrate, lanthanum chloride, and lanthanum sulfate. In some embodiments, the water-soluble lanthanum salt is preferably lanthanum nitrate.
The water-soluble yttrium salt may include at least one selected from yttrium nitrate, yttrium chloride, and yttrium acetate.
The water-soluble ytterbium salt may comprise ytterbium nitrate or ytterbium trichloride.
The water-soluble aluminum salt may include at least one selected from aluminum trichloride, aluminum trichloride hexahydrate, aluminum sulfate octadecanoate, and aluminum nitrate.
The water-soluble zirconium salt may include at least one selected from zirconium oxychloride, zirconium sulfate, or zirconium nitrate.
The molar concentration of the copper source in the copper source aqueous solution may be 0.1 to 5mol/L. In some embodiments, the molar concentration of the copper source in the aqueous copper source solution is between 0.5 and 3mol/L. In some embodiments, the molar concentration of the copper source in the aqueous copper source solution is between 0.5 and 2mol/L. In some embodiments, the molar concentration of the copper source in the aqueous copper source solution is 1-2mol/L.
The molar concentration of the precipitant in the aqueous solution containing the precipitant may be 1 to 10mol/L. In some embodiments, the molar concentration of the precipitant in the aqueous solution containing the precipitant may be 1-5mol/L. In some embodiments, the molar concentration of the precipitant in the aqueous solution containing the precipitant may be 2-4mol/L. In some embodiments, the molar concentration of the precipitant in the aqueous solution containing the precipitant may be 3-4mol/L.
The molar concentration of the oxide support precursor salt in the aqueous solution containing the oxide support precursor salt may be 0.1 to 5mol/L. In some embodiments, the molar concentration of the oxide support precursor salt in the aqueous solution of the oxide support precursor salt may be from 0.5 to 3mol/L. In some embodiments, the molar concentration of the oxide support precursor salt in the aqueous solution of the oxide support precursor salt may be from 1 to 2mol/L.
The feeding mole ratio of the complexing agent to the copper salt can be 1:1-5:1.
The molar ratio of the protective agent to the copper salt can be 1:1-5:1.
The feeding molar ratio of the reducing agent to the copper salt can be 1:1-5:1.
The feeding mole ratio of the precipitant to the copper salt may be 1:1-5:1.
The feeding mole ratio of the oxide carrier precursor salt to the copper salt is 0.5:1.0-2.0:1.0. In some embodiments, the molar ratio of the oxide support precursor salt to the copper salt is from 0.7:1.0 to 1.5:1.0. In some embodiments, the molar ratio of the oxide support precursor salt to the copper salt is from 0.8:1.0 to 1.2:1.0. In some embodiments, the molar ratio of the oxide support precursor salt to the copper salt is from 0.9:1.0 to 1.1:1.0. In some embodiments, the molar ratio of the oxide support precursor salt to the copper salt is from 0.9:1.0 to 1.0:1.0. In some embodiments, the molar ratio of the oxide support precursor salt to the copper salt is from 1.0:1.0 to 1.1:1.0.
The temperature of the first reaction may be 40 ℃ to 100 ℃. In some embodiments, the temperature of the first reaction is from 40 ℃ to 80 ℃. In some embodiments, the temperature of the first reaction is from 40 ℃ to 70 ℃. In some embodiments, the temperature of the first reaction is from 40 ℃ to 60 ℃. In some embodiments, the temperature of the first reaction is 50 ℃ to 55 ℃.
The time of the first reaction may be 2 hours to 12 hours. In some embodiments, the time of the first reaction is from 4 hours to 10 hours. In some embodiments, the time of the first reaction is from 5 hours to 8 hours. In some embodiments, the time of the first reaction is from 6 hours to 7 hours.
The temperature of the cooled water can be 15-30 ℃. In some embodiments, the reduced post-temperature is 20 ℃ to 25 ℃.
The aging time may be 2 hours to 12 hours. In some embodiments, the aging is for a period of 3 hours to 10 hours. In some embodiments, the aging is for a period of 4 hours to 8 hours. In some embodiments, the aging is for a period of 4 hours to 6 hours. In some embodiments, the aging is for a period of 4 hours to 5 hours.
The aging can be stirring at normal temperature and normal pressure (20-30 ℃ and 0.1 Mpa).
The post-processing may include: filtering, washing the filter cake with water, drying and roasting.
The drying temperature may be 80-110 ℃. In some embodiments, the temperature of the drying may be 90-110 ℃. In some embodiments, the temperature of the drying may be 100-110 ℃.
The drying time may be 5 to 20 hours. In some embodiments, the drying temperature may be 5-15 hours. In some embodiments, the drying temperature may be 6-15 hours. In some embodiments, the drying temperature may be 8-20 hours. In some embodiments, the drying temperature may be 8-15 hours. In some embodiments, the drying temperature may be 8-10 hours.
The firing temperature may be 200-700 ℃. In some embodiments, the firing temperature may be 300-600 ℃. In some embodiments, the firing temperature may be 400-500 ℃. In some embodiments, the firing temperature may be 450-500 ℃.
The firing may be performed under a nitrogen atmosphere.
The calcination time may be 2 hours to 12 hours. In some embodiments, the firing time is from 4 hours to 10 hours. In some embodiments, the firing time is from 5 hours to 8 hours. In some embodiments, the firing time is from 6 hours to 7 hours.
In a third aspect, the present invention provides a catalyst according to the first aspect or the use of the catalyst according to the second aspect.
Use of the catalyst of the first aspect or the catalyst prepared by the preparation method of the second aspect for the catalytic preparation of glycerol into hydroxyacetone. The catalyst can catalyze the preparation of glycerin into hydroxyacetone.
In a fourth aspect, the present invention provides a method for preparing hydroxyacetone.
A method for preparing hydroxyacetone, comprising: pretreating the catalyst prepared by the catalyst according to the first aspect or the catalyst prepared by the preparation method according to the second aspect with hydrogen, mixing the glycerol aqueous solution with the pretreated catalyst, and performing a second reaction in the presence of hydrogen and nitrogen to obtain the hydroxyacetone.
The weight percentage of glycerol in the aqueous glycerol solution may be 10% to 90% based on the total weight of the aqueous glycerol solution.
The second reaction may be carried out by directly mixing glycerol with the catalyst or in a continuous flow fixed bed reactor. In some embodiments, the second reaction directly mixes glycerol with a catalyst to react. In some embodiments, the second reaction is carried out in a continuous flow fixed bed reactor. In some embodiments, the second reaction is carried out in a continuous flow fixed bed reactor, where the glycerol is fed from a feed tank to the top of the catalytic dehydration reactor by a constant flow pump and flows through the catalyst bed.
The pretreatment includes hydrogen gas with a gas flow rate of 50-200mL/min, and the pretreatment is carried out at 200-500 ℃ for 1-6 hours. In some embodiments, the pretreatment comprises hydrogen gas at a gas flow rate of 100mL/min, and is treated at 400 ℃ for 2 hours to 5 hours.
The mass space velocity of the second reaction may be 0.01h -1 -1h -1 . In some embodiments, the second reaction has a mass space velocity of 0.05h -1 -0.5h -1 . In some embodiments, the second reaction has a mass space velocity of 0.1h -1 -0.5h -1 . In some embodiments, the second reaction has a mass space velocity of 0.05h -1 -0.1h -1 。
The temperature of the second reaction may be 180 ℃ to 500 ℃. In some embodiments, the temperature of the second reaction is 180 ℃ to 400 ℃. In some embodiments, the temperature of the second reaction is 180 ℃ to 300 ℃. In some embodiments, the temperature of the second reaction is 180 ℃ to 250 ℃. In some embodiments, the temperature of the second reaction is 200 ℃ to 250 ℃.
The air pressure of the second reaction may be 0.1Mpa to 5.0Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 4.0Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 3.0Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 2.0Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 1.0Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 0.5Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 0.2Mpa. In some embodiments, the gas pressure of the second reaction is between 0.1Mpa and 0.16Mpa.
The volume ratio of the hydrogen to the nitrogen in the step in the presence of the hydrogen and the nitrogen is 0.5:99.5-20:80. In some embodiments, the volume ratio of hydrogen to nitrogen in the step in the presence of hydrogen and nitrogen is from 1:99.5 to 10:90. In some embodiments, the volume ratio of hydrogen to nitrogen in the step in the presence of hydrogen and nitrogen is 1:99.5-5: 95. in some embodiments, the volume ratio of hydrogen to nitrogen in the step in the presence of hydrogen and nitrogen is from 5:99.5 to 10:98. In some embodiments, the volume ratio of hydrogen to nitrogen in the step in the presence of hydrogen and nitrogen is from 4:99.5 to 6:99.
The molar ratio of hydrogen to glycerol may be from 1:1500 to 1:50.
Advantageous effects
Compared with the prior art, the invention has at least one of the following beneficial technical effects:
(1) The reaction pressure of the catalyst provided by the invention can be at normal pressure (0.1 Mpa), so that the safety of the reaction is greatly enhanced and the requirements of equipment are reduced.
(2) The catalyst provided by the invention adopts the oxide carrier with proper acidity and alkalinity as the carrier of the elemental copper, and the oxide carrier has stronger binding force with the elemental copper than other oxide carriers, so that the elemental copper can be anchored, the agglomeration process of the metal copper is delayed, and the service life of the catalyst is prolonged. In addition, the simple substance copper and the oxide carrier can cooperatively catalyze the glycerol, and the selectivity of the glycerol to the hydroxyacetone is high, and the efficiency is high.
(3) The catalyst provided by the invention has the advantages of high glycerol conversion rate, high selectivity to hydroxyacetone, long continuous service life and the like.
(4) The catalyst provided by the invention has high conversion rate to glycerin and extremely high selectivity to hydroxyacetone in the presence of hydrogen and nitrogen, especially in the case of low hydrogen content.
Definition of terms:
in the present invention, "mass space velocity" is the ratio of the mass of the feed to the mass of the catalyst per 1 hour.
"room temperature" in the present invention means a temperature from about 10℃to about 40 ℃. In some embodiments, "room temperature" refers to a temperature from about 20 ℃ to about 30 ℃; in other embodiments, "room temperature" refers to a temperature from about 25 ℃ to about 30 ℃; in still other embodiments, "room temperature" refers to 10 ℃, 15 ℃,20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, and so forth.
In the present invention, "rpm" means the rotational speed "revolutions per minute".
In the present invention, "V/V" means a volume ratio. "wt%" means weight percent.
Detailed Description
In order to better understand the technical solution of the present invention, some non-limiting examples are further disclosed below to further describe the present invention in detail.
The reagents used in the present invention are all commercially available or can be prepared by the methods described herein.
Example 1: preparation of the catalyst
The catalyst was prepared as follows:
13.4g of copper chloride (0.1 mol) was dissolved in 100mL of water, 6.21g of ethylene glycol (0.1 mol), 6.01g of ethylenediamine (0.1 mol), and 7.6g of sodium borohydride (0.2 mol) were further added, argon was introduced and the temperature was raised to 50℃for reaction for 6 hours, and the mixture was cooled to 25℃and was designated as solution A.
6.3g of aluminum trichloride (0.047 mol) and 16.4g of zirconium sulfate (0.058 mol) were dissolved in 100ml of water and designated as solution B; 39.5g of sodium carbonate (0.373 mol) was dissolved in 100mL of water and designated as solution C. Solution B and solution C were co-current dropped to A at constant speed and under stirring at 600rpm, and stirring was continued for 5h after 1h had been dropped. Filtering the obtained product, drying at 100deg.C for 15 hr, and calcining the obtained solid at 450deg.C under nitrogen atmosphere for 2 hr to obtain catalyst, which is denoted as Cu/Al 2 O 3 -ZrO 2 A catalyst. In Cu/Al 2 O 3 -ZrO 2 The Cu/Al is based on the total weight of the catalyst 2 O 3 -ZrO 2 The catalyst comprises the following components in percentage by weight: cu:39.94%; al (Al) 2 O 3 ：15.09％；ZrO 2 ：44.97％。
Example 2: preparation of the catalyst
The catalyst was prepared as follows:
13.4g of copper chloride (0.1 mol) was dissolved in 100mL of water, 6.21g of ethylene glycol (0.1 mol), 6.01g of ethylenediamine (0.1 mol), and 7.6g of sodium borohydride (0.2 mol) were further added, argon was introduced and the temperature was raised to 50℃for reaction for 6 hours, and the mixture was cooled to 25℃and was designated as solution A.
6.3g of aluminum trichloride (0.047 mol) and 10.8g of lanthanum chloride (0.044 mol) were dissolved in 100ml of water and designated as solution B; 39.5g of sodium carbonate (0.373 mol) was dissolved in 100mL of water and designated as solution C. Solution B and solution C were co-current dropped to A at constant speed and under stirring at 600rpm, and stirring was continued for 4h after 1h had been dropped. Filtering the obtained product, drying at 100deg.C for 8 hr, and calcining the obtained solid at 450deg.C under nitrogen atmosphere for 6 hr to obtain catalyst, which is denoted as Cu/Al 2 O 3 -La 2 O 3 A catalyst. In Cu/Al 2 O 3 -La 2 O 3 The Cu/Al is based on the total weight of the catalyst 2 O 3 -La 2 O 3 The catalyst comprises the following components in percentage by weight: cu:35% -40%; al (Al) 2 O 3 ：12％～20％；ZrO 2 ：40％～50％。
Example 3: preparation of the catalyst
The procedure of example 2 was repeated except that "10.8g lanthanum chloride (0.044 mol)" in example 2 was replaced with "16.9g yttrium nitrate (0.044 mol)", and the catalyst obtained was designated Cu/Al 2 O 3 -Y 2 O 3 A catalyst. In Cu/Al 2 O 3 -Y 2 O 3 The Cu/Al is based on the total weight of the catalyst 2 O 3 -Y 2 O 3 The catalyst comprises the following components in percentage by weight: cu:35% -40%; al (Al) 2 O 3 ：12％～20％；Y 2 O 3 ：40％～50％。
Example 4: preparation of the catalyst
The procedure of example 2 was repeated except that "10.8g lanthanum chloride (0.044 mol)" in example 2 was replaced with "15.8g ytterbium nitrate (0.044 mol)", and the catalyst obtained was designated Cu/Al 2 O 3 -Yb 2 O 3 A catalyst. In Cu/Al 2 O 3 -Yb 2 O 3 The Cu/Al is based on the total weight of the catalyst 2 O 3 -Yb 2 O 3 The catalyst comprises the following components in percentage by weight: cu:40% -50%; al (Al) 2 O 3 ：15％～20％；Yb 2 O 3 ：30％～40％。
Comparative example 1: preparation of the catalyst
The procedure of example 2 was repeated except that "10.8g lanthanum chloride (0.044 mol)" in example 2 was replaced with "7.1g zinc sulfate (0.044 mol)", and the catalyst obtained was designated Cu/Al 2 O 3 -ZnO catalyst. In Cu/Al 2 O 3 -ZnO catalyst, based on the total weight of the Cu/Al catalyst 2 O 3 The ZnO catalyst comprises the following components in percentage by weight: cu:45% -55%; al (Al) 2 O 3 ：15％～25％；ZnO：25％～35％。
Comparative example 2: preparation of the catalyst (cf. CN 112090424A)
The catalyst is prepared by adopting a coprecipitation method: according to the stoichiometric ratio, a proper amount of copper nitrate trihydrate, anhydrous zirconium nitrate and ammonium metatungstate are respectively dissolved according to the mass ratio of 1:4 with deionized water, and then the three solutions are mixed. Then dripping 20wt% of Na with a peristaltic pump at a certain rate under the mechanical stirring condition of 800r/min 2 CO 3 The solution was subjected to coprecipitation reaction by adjusting the ph=9 of the reaction solution, and the reaction was continued for 1 hour. Standing and aging for 2 hours at normal temperature and normal pressure, and then washing with deionized water for 5 times. Drying the filter cake in the shade at room temperature (25+/-3 ℃) and extruding to form strips, then fully drying at 120 ℃, and roasting at 600 ℃ for 4 hours in air atmosphere to obtain the catalyst A. Catalyst A is prepared by ZrO 2 Is a carrier and comprises 18% of CuO and 20% of WO based on the mass of the carrier 3 。
Comparative example 3: preparation of the catalyst
Reference was made to the selective hydrogenolysis of glycerol to propylene glycol on a "magnesium aluminum composite oxide supported copper catalyst" (Wang Shuai et al, chemical journal, 2012, 70, 1897-1903) to prepare a 4% copper loaded highly dispersed copper/magnesium aluminum composite oxide catalyst.
Preparation of magnesium-aluminum composite oxide: the magnesium-aluminum composite oxide is prepared by coprecipitation method, and Mg (NO) is added according to the ratio of Mg/Al atomic ratio of 3/1 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 O is dissolved in 40mL of water to prepare mixed salt solution, mg 2+ And Al 3+ Is at a final concentration ofPreparing 40mL of mixed alkali solution from sodium hydroxide and sodium carbonate according to the concentration of 0.34mol/L and 0.060mol/L respectively, slowly dripping the mixed salt solution and the mixed alkali solution into 20mL of deionized water under electromagnetic stirring, keeping the pH value of the solution between 9 and 10, continuing stirring for 12 hours for aging, filtering, washing with water and pumping, and drying at 110 ℃ for 12 hours to obtain the magnesium aluminum hydrotalcite precursor. Grinding the magnesium-aluminum hydrotalcite precursor, and roasting at 400 ℃ for 4 hours to obtain the magnesium-aluminum composite oxide.
Preparation of 4% copper loaded high dispersion copper/magnesium aluminum composite oxide catalyst: 2.51g of copper acetate is taken and ultrasonically dissolved in 20mL of ethanol, 17.49g of magnesium-aluminum composite oxide is added, stirring is carried out for 12 hours, the ethanol is rapidly removed by a rotary evaporator, drying is carried out for 12 hours at 110 ℃, and roasting is carried out for 4 hours at 400 ℃, thus obtaining the high-dispersion copper/magnesium-aluminum composite oxide catalyst with 4% copper loading.
Example 5: preparation of hydroxyacetone (under the atmosphere of Hydrogen-Nitrogen mixture)
1) Taking the catalysts obtained in examples 1-4 and comparative example 1 respectively, and pretreating with hydrogen with the air flow rate of 100mL/min at 400 ℃ for 2 hours to obtain an activated catalyst;
2) In a continuous flow fixed bed reactor which has been charged with the activated catalyst obtained in said step 1), the mass space velocity of the aqueous solution containing 10% by weight of glycerin was controlled to be 0.1h -1 The reaction temperature was 220℃and the reaction pressure was 0.10MPa, and an aqueous solution containing 10wt% of glycerin was mixed with a hydrogen-nitrogen mixture (hydrogen: nitrogen=5:95 (V/V)), and dehydrated to obtain hydroxyacetone, and the glycerin conversion, hydroxyacetone selectivity, 1,2 propylene glycol selectivity and hydroxyacetone yield were calculated. The results are shown in Table 1.
Table 1: evaluation results of catalyst Performance obtained in examples 1 to 4 and comparative examples 1 to 3
Analysis of results:
(1) The catalysts obtained in examples 1-4 have high glycerol conversion, high selectivity to hydroxyacetone, and long service life. The catalysts obtained in comparative examples 1-3 have low glycerol conversion under the above reaction conditions, low selectivity to hydroxyacetone, and short continuous service life.
(2) The catalyst obtained in the examples 1-4 has high glycerol conversion rate and selectivity to hydroxyacetone under the condition of reaction pressure of 0.1MPa, high safety and excellent beneficial effects.
While the methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and combinations of the methods and applications described herein can be made and applied within the spirit and scope of the invention. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention.
Claims (7)
1. The catalyst is characterized by comprising a metal active component and an oxide carrier, wherein the metal active component is loaded on the oxide carrier, the metal active component is elemental copper, the oxide carrier comprises an oxide carrier I and aluminum oxide, the oxide carrier I is at least one of lanthanum oxide, yttrium oxide and ytterbium oxide, the weight percentage of the metal active component is 35% -47% based on the total weight of the catalyst, the weight percentage of the aluminum oxide is 13% -18%, and the balance is the oxide carrier I, and the catalyst comprises the following steps: mixing a complexing agent, a protective agent and a reducing agent with a copper source aqueous solution, wherein the copper source aqueous solution is a copper salt-containing aqueous solution, performing a first reaction under the protection of inert gas, cooling, adding a precipitant-containing aqueous solution and an oxide carrier precursor salt-containing aqueous solution for aging, and performing aftertreatment to obtain the catalyst; the complexing agent comprises at least one selected from methylamine, ethylenediamine, sodium nitrilotriacetate and disodium ethylene diamine tetraacetate; and/or the protective agent comprises at least one selected from ethanol, glycol and glycerol; and/or the reducing agent comprises at least one selected from hydrazine hydrate, sodium borohydride and potassium borohydride; and/or the inert gas comprises at least one selected from nitrogen and argon; and/or the precipitant comprises at least one selected from sodium hydroxide, urea, ammonia water, ammonium bicarbonate, ammonium carbonate, sodium carbonate and potassium carbonate.
2. The catalyst of claim 1, wherein the metal active component is present in an amount of 10% to 70% by weight, based on the total weight of the catalyst, with the balance being the oxide support.
3. The catalyst of claim 1, the copper salt being a water-soluble copper salt; and/or the water-soluble copper salt comprises at least one selected from copper nitrate, copper sulfate and copper chloride.
4. The catalyst of claim 1, the oxide support precursor salt comprising at least one selected from the group consisting of water-soluble lanthanum salts, water-soluble yttrium salts, and water-soluble ytterbium salts, water-soluble aluminum salts, and water-soluble zirconium salts.
5. The catalyst of claim 1, wherein the temperature of the first reaction is 40 ℃ to 100 ℃; and/or the time of the first reaction is 2 hours to 12 hours; and/or the temperature of the cooled water is 15-30 ℃; and/or the aging time is 2 hours to 12 hours; and/or the post-processing comprises: filtering, washing the filter cake with water, drying, and roasting at 200-700 deg.C for 2-12 hr.
6. Use of the catalyst according to claim 1 for the catalytic preparation of glycerol as hydroxyacetone.
7. A method for preparing hydroxyacetone, comprising: pretreating the catalyst of claim 1 with hydrogen, mixing glycerol with the pretreated catalyst, and performing a second reaction in the presence of hydrogen and nitrogen to obtain the hydroxyacetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110933409.9A CN113617345B (en) | 2021-08-13 | 2021-08-13 | Catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110933409.9A CN113617345B (en) | 2021-08-13 | 2021-08-13 | Catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113617345A CN113617345A (en) | 2021-11-09 |
| CN113617345B true CN113617345B (en) | 2023-07-28 |
Family
ID=78385411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110933409.9A Active CN113617345B (en) | 2021-08-13 | 2021-08-13 | Catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113617345B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116510736B (en) * | 2023-05-09 | 2023-10-13 | 中国科学院兰州化学物理研究所 | Supported nano copper-based catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654797A (en) * | 2008-08-19 | 2010-02-24 | 陈允盈 | Chemical-copper plating liquid and copper plating production process |
| CN101927200A (en) * | 2010-08-26 | 2010-12-29 | 河南煤业化工集团有限责任公司 | Method for activating and reducing catalyst for hydrogenation of dimethyl oxalate to prepare glycol |
| CN103242149A (en) * | 2013-05-15 | 2013-08-14 | 常州工学院 | Method for selectively preparing acraldehyde and hydroxy-acetone |
| CN104722301A (en) * | 2015-03-04 | 2015-06-24 | 浙江工业大学之江学院 | Preparation method of catalyst for preparing dihydroxy acetone by selective oxidation of glycerinum and application method thereof |
| CN113058608A (en) * | 2020-01-02 | 2021-07-02 | 万华化学集团股份有限公司 | Catalyst for preparing isopropylbenzene by hydrogenolysis of alpha-dimethyl benzyl alcohol and preparation method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336591C (en) * | 2005-09-09 | 2007-09-12 | 汕头大学 | Catalyst for selective reduction of No by propylene in oxygen-rich condition and preparation method thereof |
| US7824574B2 (en) * | 2006-09-21 | 2010-11-02 | Eltron Research & Development | Cyclic catalytic upgrading of chemical species using metal oxide materials |
| JP5187675B2 (en) * | 2007-06-12 | 2013-04-24 | 国立大学法人 千葉大学 | Method for producing hydroxyketone from trivalent or higher alcohol and catalyst used therefor |
| CN101259415A (en) * | 2008-04-25 | 2008-09-10 | 清华大学 | Preparation of CO hydrogenation synthesizing low carbon mixed alcohol catalyst |
| CN102173977B (en) * | 2011-03-10 | 2014-03-12 | 江苏大学 | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol |
| CN103664521B (en) * | 2012-08-31 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method of glycerine hydrogenation 1,2-PD |
| US9865434B2 (en) * | 2013-06-05 | 2018-01-09 | Applied Materials, Inc. | Rare-earth oxide based erosion resistant coatings for semiconductor application |
| CN104190458B (en) * | 2014-07-16 | 2016-08-24 | 上海工程技术大学 | A kind of low temperature preparation technology of dual element modified nano-titanium dioxide colloidal sol |
| CN106140161B (en) * | 2016-07-06 | 2018-08-21 | 江苏大学 | A kind of preparation method and application of the rodlike xerogel catalyst of copper/zirconium oxide |
| CN106179366B (en) * | 2016-07-07 | 2019-01-18 | 淮安万邦香料工业有限公司 | A kind of CuO-CeO2-SiO2-Al2O3Catalyst and preparation method thereof prepares the application in 1,2- propylene glycol in glycerine hydrogenation with it |
| CN110215920A (en) * | 2019-07-03 | 2019-09-10 | 中溶科技股份有限公司 | Preparing isopropyl alcohol by acetone hydrogenation catalyst and its preparation method and application |
| CN114247451B (en) * | 2021-12-31 | 2023-12-22 | 厦门欧米克生物科技有限公司 | Glycerol hydrogenation catalyst and preparation method and application thereof |
-
2021
- 2021-08-13 CN CN202110933409.9A patent/CN113617345B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654797A (en) * | 2008-08-19 | 2010-02-24 | 陈允盈 | Chemical-copper plating liquid and copper plating production process |
| CN101927200A (en) * | 2010-08-26 | 2010-12-29 | 河南煤业化工集团有限责任公司 | Method for activating and reducing catalyst for hydrogenation of dimethyl oxalate to prepare glycol |
| CN103242149A (en) * | 2013-05-15 | 2013-08-14 | 常州工学院 | Method for selectively preparing acraldehyde and hydroxy-acetone |
| CN104722301A (en) * | 2015-03-04 | 2015-06-24 | 浙江工业大学之江学院 | Preparation method of catalyst for preparing dihydroxy acetone by selective oxidation of glycerinum and application method thereof |
| CN113058608A (en) * | 2020-01-02 | 2021-07-02 | 万华化学集团股份有限公司 | Catalyst for preparing isopropylbenzene by hydrogenolysis of alpha-dimethyl benzyl alcohol and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113617345A (en) | 2021-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102570390B1 (en) | Ammonia decomposition catalyst, and method for ammonia decomposing and hydrogen producing using the same | |
| TW200536606A (en) | Modified catalysts and process | |
| JPH11513305A (en) | Production method of epoxidation catalyst | |
| JP5999548B2 (en) | Photocatalyst and method for producing the same | |
| KR101359990B1 (en) | Catalyst for Reforming of Methane with the Enhanced Stability for Sulfur components, Preparing Method Thereof and Methane Reforming Method Using The Catalyst | |
| CN113617345B (en) | Catalyst and preparation method and application thereof | |
| WO2021120928A1 (en) | Method for preparing ni-x based oxide catalyst and use thereof in transfer dygrogenation | |
| JP2010017649A (en) | Highly active catalyst and its preparing method | |
| KR101985366B1 (en) | Composite oxide | |
| JP2023536795A (en) | Cerium-zirconium composite oxide with gradient distribution of elements and method for preparing the same | |
| CN111790431A (en) | With Al2O3Modified g-C3N4Preparation method of photocatalytic material | |
| JP3865848B2 (en) | Catalyst for methanol synthesis | |
| JP6272609B2 (en) | Method for producing composite oxide and composite oxide catalyst | |
| CN105214672A (en) | A kind of preparation method of the catalyst for methanol that maximizes | |
| JP5831946B2 (en) | Catalyst production method | |
| CN104028276A (en) | Method for preparing composite wide-temperature methanation catalyst | |
| JPH0535017B2 (en) | ||
| JP2009507627A (en) | Method for producing noble metal-containing metal oxide | |
| JP7161664B2 (en) | Method for producing catalyst for hydrogen production | |
| CN112194169A (en) | Preparation method of cerium oxide with specific mixed valence state | |
| CN106853368A (en) | The dehydrogenation of CO unstripped gas refined catalyst, Preparation method and use | |
| CN117427643B (en) | Photocatalytic material based on graphite-phase carbon nitride and preparation method and application thereof | |
| CN116747851B (en) | Spherical catalyst for synthesizing hydrogen peroxide by anthraquinone process and preparation method thereof | |
| CN114551910B (en) | Composite rare earth oxide and preparation method and application thereof | |
| CN109482224B (en) | Iridium dioxide composite nitrogen-doped mesoporous carbon nano catalyst, preparation method thereof and method for synthesizing gluconic acid by catalytic oxidation of glucose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |