CN111348987A - Reduction method of catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation - Google Patents
Reduction method of catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation Download PDFInfo
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Abstract
The invention provides a reduction method of a catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation, which comprises the following four stages under a reducing atmosphere: 1) the first stage is as follows: heating to 70 deg.c at a rate of less than 10 deg.c/hr; 2) and a second stage: heating to 120 deg.c at a rate of less than 5 deg.c/hr; then keeping the temperature constant; 3) and a third stage: heating to 180 deg.c at a rate of less than 3 deg.c/hr; then keeping the temperature constant; 4) a fourth stage: heating to 210 deg.c at a rate of less than 5 deg.c/hr; then keeping the temperature constant; wherein the volume concentration of the reducing gas in the reducing atmosphere is 10-30 v%. The reduction method has the advantages that the temperature rise of the catalyst bed layer is not obvious in the reduction process, and the technical problems that the catalyst bed layer is easy to fly in temperature, the pressure drop of the bed layer is increased after reduction, the activity of the catalyst is poor in reaction, the selectivity of a target product is poor and the like in the reduction process are well solved.
Description
Technical Field
The invention relates to a reduction method of a catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation, in particular to a reduction method of a copper-based catalyst.
Background
Glycol is also known as glycol, is a colorless, odorless and sweet liquid, and can be mutually dissolved with water in any proportion. The ethylene glycol has wide application, is an important organic chemical synthesis raw material, is mainly used for manufacturing polyester fibers, antifreeze, nonionic surfactant, ethanolamine, explosive and the like, is also used for preparing low-freezing-point cooling liquid (for engines), and can be directly used as a solvent. In addition, it has wide application in tobacco industry, textile industry and cosmetic industry.
At present, the method for producing ethylene glycol at home and abroad mainly adopts a petroleum-ethylene oxide route. The direct hydration process with ethylene oxide, also known as pressurized hydration process, has insurmountable disadvantages, mainly manifested by long process flow, large water ratio (molar ratio of water to ethylene oxide), high energy consumption, and poor ethylene glycol selectivity. Because the petroleum resources in China are limited and the natural gas and coal resources are relatively rich, the development of a process route for preparing the ethylene glycol by preparing the synthesis gas from the natural gas and coal resources has great significance for reducing the energy consumption of ethylene and saving the petroleum energy. The route of preparing ethylene glycol from synthesis gas by an oxalate method is a hotspot of current research due to mild reaction conditions and high ethylene glycol selectivity. The research is carried out by various companies and research institutions at home and abroad, such as DuPont, Seffolon, ARCO, Uyu Xingsheng, UCC, carbon chemical laboratory of Tianjin university, Fujian Chinese academy of sciences and the Huadong university, wherein the development of the catalyst for preparing the ethylene glycol by hydrogenating dimethyl oxalate is one of the difficulties of the project.
Many patents relating to catalysts for synthesizing ethylene glycol or glycolate by hydrogenating oxalate have been reported, such as CN1194268, CN101474561, CN101607205, CN101590407, etc., and all of these patents address the preparation technology of catalysts for preparing ethylene glycol by hydrogenating oxalate. However, in many documents relating to the catalyst for preparing ethylene glycol by hydrogenating oxalate, the reduction method or process is rarely described in detail.
Has been reported in the literature and found inWhen the copper-based catalyst is reduced, an improper reduction activation scheme or improper operation is adopted, so that the sintering of the catalyst influences the service activity and the service life of the catalyst, and even the mechanical strength is reduced or the pressure drop in a reactor is increased due to direct partial crushing. In addition, different catalytic reactions have different active centers, and excessive reduction or insufficient reduction can cause damage to the catalyst. It has been reported that the hydrogenation of dimethyl oxalate to ethylene glycol is Cu0And Cu+As a result of the synergistic effect, Cu+Determination of dimethyl oxalate conversion, Cu0The ethylene glycol selectivity is determined. Therefore, the proper reduction scheme of the catalyst for preparing ethylene glycol by hydrogenating dimethyl oxalate directly influences the using effect of the catalyst.
The copper-based catalyst is industrially used in a large amount in hydrogen reduction, and although other reported methods are mainly classified into a gas-phase reduction method and a liquid-phase reduction method. The traditional process of gas phase reduction activation of a copper-based catalyst is often accompanied by strong heat effect, so that the problems of long time consumption, difficult control of reduction conditions and the like exist in the catalyst activation process; the liquid phase reduction method is often not technically complete and has high production cost, and large-scale industrial application is difficult to realize.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a method for reducing a catalyst in the preparation of ethylene glycol by gas-phase hydrogenation of dimethyl oxalate, which comprises the following four stages under a reducing atmosphere: 1) the first stage is as follows: heating to 70 deg.c at a rate of less than 10 deg.c/hr; 2) and a second stage: heating to 120 deg.c at a rate of less than 5 deg.c/hr; then keeping the temperature constant; 3) and a third stage: heating to 180 deg.c at a rate of less than 3 deg.c/hr; then keeping the temperature constant; 4) a fourth stage: heating to 210 deg.c at a rate of less than 5 deg.c/hr; and then keeping the temperature constant. The reduction method solves the technical problems that a catalyst bed layer is easy to fly warm, the pressure drop of the bed layer is increased after reduction, the activity of the catalyst is poor during reaction, the selectivity of a target product is poor and the like.
In order to achieve the above objects and other related objects, the present invention is achieved by the following technical solutions:
the invention provides a reduction method of a catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation, which comprises the following four stages under a reducing atmosphere:
1) the first stage is as follows: heating to 70 ℃, wherein the heating rate is less than 10 ℃/h, such as 1-6 ℃/h and 6-8 ℃/h;
2) and a second stage: heating to 120 ℃, wherein the heating rate is less than 5 ℃/h, such as 0.5-2 ℃/h and 2-4 ℃/h; then keeping the temperature constant;
3) and a third stage: heating to 180 ℃, wherein the heating rate is less than 3 ℃/h, such as 0.5-1 ℃/h and 1-2 ℃/h; then keeping the temperature constant;
4) a fourth stage: heating to 210 ℃, wherein the heating rate is less than 5 ℃/hour, such as 1-3 ℃/hour or 3-4 ℃/hour; then keeping the temperature constant;
wherein the volume concentration of the reducing gas in the reducing atmosphere is 10 v% -30 v%, such as 10 v% -20 v% or 20 v% -30 v%.
Preferably, the gas providing the reducing atmosphere comprises a reducing gas selected from H2And CO.
Preferably, the gas providing the reducing atmosphere comprises an inert gas selected from at least one of nitrogen and argon.
Preferably, in the step 2), the temperature is kept constant for 4 to 8 hours, such as 4 to 6 hours or 6 to 8 hours.
Preferably, in the step 3), the temperature is kept constant for 8 to 16 hours, such as 8 to 12 hours or 12 to 16 hours.
Preferably, in step 3), when entering the third stage, methanol is introduced; in the step 4), methanol is continuously introduced when the fourth stage is carried out.
More preferably, the liquid hourly space velocity of methanol is 0.05-0.20 g/ml cat.h, such as 0.05-0.10 g/ml cat.h or 0.10-0.20 g/ml cat.h.
Preferably, in the step 4), the temperature is kept constant for 4 to 8 hours, such as 4 to 6 hours or 6 to 8 hours.
Preferably, the reduction hourly space velocity is 2000-6000 h-1E.g. 2000 to 4000h-1Or 4000 to 6000h-1The pressure is 0.5-3.0 MPa, such as 05 to 2.0MPa or 2.0 to 3.0 MPa.
Preferably, the catalyst comprises the following components in percentage by mass:
20 to 70 wt% of CuO, such as 20 to 45 wt% or 45 to 70 wt%;
SiO225 to 79 wt%, such as 25 to 52 wt% or 52 to 79 wt%;
1.0-5.0 wt% of metal assistant oxide, such as 1.0-3.0 wt% or 3.0-5.0 wt%; the metal auxiliary agent is selected from metal elements Li, Na, K, Cs, Ba, Mn, Ni, Al, Ag and Zn.
Compared with the prior art, the invention has the following advantages:
the method for reducing the catalyst in the preparation of the ethylene glycol by gas-phase hydrogenation of dimethyl oxalate adopts the volume concentration of the reducing gas of 10-30 v percent and has proper temperature rise rate, reduction airspeed and temperature, so that the problems of long reduction time and easy temperature runaway of a bed layer can be well solved, the pressure drop of the bed layer after reduction cannot rise, and the selectivity of the ethylene glycol after reaction is high. Preferably, the catalyst exposed to water vapor on the catalyst bed is reduced in the chance of repeated oxidation-reduction reactions by means of methanol addition during the reduction process, increasing the activity of the catalyst.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The reduction activation reaction of the catalyst and the hydrogenation reaction of the reduced feed in the following examples are carried out in a simulated industrial gas phase hydrogenation reactor, the simulated hydrogenation reactor is a reaction tube inserted with a thermowell, and the size of an internal single tube is phi 45 × 3 × 5200 mm.
In the following examples, about 5.0L of a dimethyl oxalate hydrogenation catalyst was charged into a single-tube reactor. The catalyst filling height is 4500mm, and the catalyst bed200mm ceramic balls are arranged under the bed layer, and 500mm ceramic balls are arranged on the bed layer. The start-up and shut-down of each example followed the bench-scale operation of a modular hydrogenation reactor. Before the temperature of the reactor is raised, H with certain flow is respectively introduced through two gas mass flowmeters2And N2The flow rate of the two gases is reduced by reducing H in the mixed gas2Concentration determination, e.g. 10% to 30% H2And the rest volume percentage is nitrogen. When the system pressure reaches the required reduction pressure, the introduced gas is stopped, the circulating compressor is started to establish balance, and the circulating flow of the compressor is determined by the reduction space velocity. In the temperature-rising reduction stage, the hydrogen concentration in the reduction mixed gas is reduced because the reduction reaction consumes the hydrogen, and the reduction gas H is supplemented2In the system of H2Concentration maintenance of the required H in the reducing conditions employed in each example2After the reduction of dimethyl oxalate hydrogenation catalyst is completed according to the method of said invention, △ P of model hydrogenation reactor is not greater than 100KPa, and the system utilizes H extraction process2The concentration becomes pure hydrogen atmosphere, the temperature and the pressure are adjusted to be proper feeding temperature and pressure, and the feeding reaction of the dimethyl oxalate and the hydrogen is waited.
Example 1
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; 3.0 wt% of an oxide of metal K. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is raised to a first stage at room temperature to 70 ℃, and the heating rate is controlled to be 8 ℃/h; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the constant temperature is kept for 8 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 16 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 8 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein, theThe reducing mixed gas comprises reducing gas H2And nitrogen, the volume concentration of the reducing gas is 20 v%, and the space velocity is 2000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 2
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; oxide of metallic Ag 3.0 wt%. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is increased to a first stage at room temperature to 70 ℃, and the temperature increase rate is controlled to be 6 ℃/h; in the second stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 120 ℃, and the constant temperature is kept for 4 hours; in the third stage, the temperature rise rate is controlled to be 1 ℃/hour, the temperature is raised to 180 ℃, the temperature is kept constant for 8 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 3 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 4 h, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen, the volume concentration of the reducing gas is 20 v%, and the space velocity is 6000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 3
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; 3.0 wt% of metallic Ni oxide. The reduction method of the catalyst is carried out in a reducing atmosphereThe following four stages are included: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is raised to a first stage at room temperature to 70 ℃, and the heating rate is controlled to be 1 ℃/hour; in the second stage, the temperature rise rate is controlled to be 0.5 ℃/hour, the temperature is raised to 120 ℃, and the temperature is kept for 6 hours; in the third stage, the temperature rise rate is controlled to be 0.5 ℃/hour, the temperature is raised to 180 ℃, the temperature is kept constant for 12 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 1 ℃/hour, the temperature is raised to 210 ℃, the temperature is kept constant for 6 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen, the volume concentration of the reducing gas is 20 v%, and the space velocity is 4000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 4
The loaded catalyst comprises the following components in percentage by mass: 20 wt% of CuO; SiO 2279 wt%; 1.0 wt% of an oxide of metallic Mn. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is raised to a first stage at room temperature to 70 ℃, and the heating rate is controlled to be 8 ℃/h; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the temperature is kept for 6 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 12 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 6 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen gasThe volume concentration of the reducing gas is 10 v%, and the airspeed is 4000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 5
The loaded catalyst comprises the following components in percentage by mass: 70 wt% of CuO; SiO 2225 wt%; 5.0 wt% of metallic Zn oxide. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is raised to a first stage at room temperature to 70 ℃, and the heating rate is controlled to be 8 ℃/h; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the temperature is kept for 6 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 12 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 6 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen, the volume concentration of the reducing gas is 30 v%, and the space velocity is 4000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 6
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; 3.0 wt% of an oxide of metal K. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: to the deviceThe preheater, the steam drum and the reactor are heated simultaneously, the temperature is raised to a first stage, the room temperature is 70 ℃, and the temperature raising rate is controlled to be 8 ℃/hour; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the temperature is kept for 6 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 12 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.05g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 6 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.05g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen, the volume concentration of the reducing gas is 20 v%, and the space velocity is 4000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 7
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; oxide of metallic Ag 3.0 wt%. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is raised to a first stage at room temperature to 70 ℃, and the heating rate is controlled to be 8 ℃/h; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the temperature is kept for 6 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 12 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.20g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 6 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.20g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And argon, the volume concentration of the reducing gas is 20 v%, and the space velocity is 4000h-1And the pressure is 2.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 8
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; 3.0 wt% of metallic Ni oxide. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: simultaneously heating a preheater, a steam drum and a reactor of the device, wherein the temperature is raised to a first stage at room temperature to 70 ℃, and the heating rate is controlled to be 8 ℃/h; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the temperature is kept for 4 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 8 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept for 4 h, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen, the volume concentration of the reducing gas is 20 v%, and the space velocity is 4000h-1The pressure is 3.0 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the solution is stabilized for a period of time, the temperature is adjusted to 185 ℃, dimethyl oxalate enters a reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Example 9
The loaded catalyst comprises the following components in percentage by mass: 45 wt% of CuO; SiO 2252 wt%; 3.0 wt% of metallic Ni oxide. The reduction method of the catalyst comprises the following four stages under a reducing atmosphere: the first stage is as follows: heating the preheater, steam drum and reactor simultaneously, the first stage of heating to room temperature of 70 deg.C, and controllingThe heating rate is 8 ℃/h; in the second stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 120 ℃, and the constant temperature is kept for 8 h; in the third stage, the temperature rise rate is controlled to be 2 ℃/h, the temperature is raised to 180 ℃, the temperature is kept constant for 16 hours, methanol is pumped into the reactor from the front of a preheater by a liquid metering pump at the liquid hourly space velocity of 0.10g/mlcat.h, and the circulating gas is combined and enters the reactor; in the fourth stage, the temperature rise rate is controlled to be 4 ℃/h, the temperature is raised to 210 ℃, the temperature is kept constant for 8 hours, and methanol is pumped into the reactor by a liquid metering pump at a liquid hourly space velocity of 0.10g/ml cat.h; wherein the reducing mixed gas comprises a reducing gas H2And nitrogen, the volume concentration of the reducing gas is 20 v%, and the space velocity is 4000h-1And the pressure is 0.5 MPa. After the reduction is complete, the addition of methanol is stopped, the temperature is maintained at 210 ℃ and H is gradually added2After the concentration is increased to 100 percent and the reaction system is stabilized for a period of time, the reaction system is slowly pressurized to 3.0MPa, the temperature is adjusted to 185 ℃, dimethyl oxalate enters the reaction system at a liquid hourly space velocity of 0.70g/mlcat.h to carry out hydrogenation reaction with hydrogen, and the reaction hydrogen-ester ratio is 80. The reaction results are shown in Table 1.
Table 1 results of the reactions of example 1 to example 9
Note: DMO is dimethyl oxalate, EG is ethylene glycol, MG is methyl glycolate, BDO is 1, 2-butanediol, ET is ethanol; c represents conversion and S represents selectivity.
The catalyst is applied to the process of preparing the ethylene glycol by dimethyl oxalate gas-phase hydrogenation: dimethyl oxalate DMO is hydrogenated to methyl glycolate MG and then to ethylene glycol EG, and the ethylene glycol EG is over-hydrogenated to generate ethanol ET and 1, 2-butanediol BDO.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A reduction method of a catalyst in preparation of ethylene glycol by dimethyl oxalate gas phase hydrogenation is characterized by comprising the following four stages in a reduction atmosphere:
1) the first stage is as follows: heating to 70 deg.c at a rate of less than 10 deg.c/hr;
2) and a second stage: heating to 120 deg.c at a rate of less than 5 deg.c/hr; then keeping the temperature constant;
3) and a third stage: heating to 180 deg.c at a rate of less than 3 deg.c/hr; then keeping the temperature constant;
4) a fourth stage: heating to 210 deg.c at a rate of less than 5 deg.c/hr; then keeping the temperature constant;
wherein the volume concentration of the reducing gas in the reducing atmosphere is 10-30 v%.
2. Reduction process according to claim 1, characterized in that the gas providing the reducing atmosphere comprises a reducing gas selected from H2And CO.
3. A reducing method according to claim 1, wherein a gas for providing said reducing atmosphere includes an inert gas selected from at least one of nitrogen and argon.
4. A reduction process according to claim 1, wherein in step 2), the temperature is maintained for 4 to 8 hours.
5. A reduction process according to claim 1, wherein in step 3), the temperature is maintained for 8 to 16 hours.
6. A reduction process according to claim 1, wherein in step 3), methanol is introduced when entering the third stage; in the step 4), methanol is continuously introduced when the fourth stage is carried out.
7. A reduction process according to claim 6, wherein the liquid hourly space velocity of methanol is from 0.05 to 0.20g/ml cat.
8. A reduction process according to claim 1, wherein in step 4), the temperature is maintained for 4 to 8 hours.
9. The reduction method according to claim 1, wherein the reduction hourly space velocity is 2000 to 6000h-1The pressure is 0.5 to 3.0 MPa.
10. A reduction process according to claim 1, wherein the catalyst comprises the following components in mass percent:
CuO 20～70wt％；
SiO225～79wt％；
1.0-5.0 wt% of an oxide of a metal additive;
the metal auxiliary agent is selected from metal elements Li, Na, K, Cs, Ba, Mn, Ni, Al, Ag and Zn.
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