AU2019323492A1 - Catalyst used for producing methyl glycolate and preparation method and application thereof - Google Patents
Catalyst used for producing methyl glycolate and preparation method and application thereof Download PDFInfo
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Abstract
A catalyst used for producing methyl glycolate by using dimethyl oxalate plus hydrogen and a preparation method and an application thereof. The catalyst comprises the following components in percentage by weight: 65-90% of silicon dioxide, 5-20% of silver elements, 0.1-5% of nickel elements, 0.01-5% of lanthanum elements, and 0.01-5% of metal element M, wherein the metal element M is selected from one of titanium, cerium, cobalt, or zirconium, and the elements exist in the form of being bound with oxygen. Compared with the prior art, the preparation method has the characteristics such as simple process and easy control of the preparation process; and the hydrogenation catalyst prepared by the method has the characteristics such as high activity, long life, and wide range of reaction operation conditions.
Description
FIELD OF THE INVENTION The invention relates to catalyst, particularly to a catalyst for producing methyl glycolate and preparation method thereof.
BACKGROUND OF THE INVENTION Methyl glycolate is the simplest hydroxy carboxylate. As an important intermediate of chemical raw materials and excellent solvent, methyl glycolate has
the following uses as an intermediate: preparing ethylene glycol by hydrogenation,
preparing glycolic acid by hydrolysis, preparing dimethyl malonate by
carbonylation, preparing glycine by ammonolysis, etc. Methyl glycolate is widely
used in chemical industry, medicine, dyes and other fields, and has broad
application prospects.
At present, the main production processes of methyl glycolate at home and
abroad include carbonylation and esterification of formaldehyde, hydrolysis of
chloroacetic acid, addition of formaldehyde and formonitrile, coupling of methyl
formate and formaldehyde, free radical addition of methylal and formaldehyde, etc,
which generally have disadvantages such as high pollution, high energy
consumption, high toxicity, corrosion of equipment and so on. As a result, there is
no mature process route in China. At present, a process including reaction of a
mixture of chloroacetic acid and caustic soda solution and then esterification is still
used in the production of methyl glycolate in China, which is characterized by
serious corrosion, heavy pollution, low yield, high cost and high impurity content of
product. In view of the shortcomings of high energy consumption, heavy pollution
and high cost of domestic routes, it is urgent to develop an environmentally friendly
synthesis and process route.
In recent years, great breakthroughs have been made in the production of
ethylene glycol (EG) from coal or natural gas, especially in the process of coupling
CO with methyl nitrite to synthesize dimethyl oxalate and then hydrogenating dimethyl oxalate to prepare ethylene glycol. At present, many sets of industrial plants have been running smoothly. Under this background, the hydrogenation of dimethyl oxalate to methyl glycolate will make full use of China's abundant coal and natural gas resources and develop C1 chemistry, and is an economic, environmentally friendly, sustainable production route in line with China's national conditions.
Domestic research institutes and enterprises have carried out the research on
the production process of methyl glycolate from oxalate by hydrogenation, and have
made some progress. Chinese patent application CN105585483A disclosed a
method to synthesize glycolate. Under the conditions of reaction temperature of
150-240 C, reaction pressure of 0.5-4 MPa, weight space velocity of oxalate of
0.1-3 h-', molar ratio of hydrogen and oxalate of (10-160):1, the effluent containing
glycolate was generated. The conversion of oxalate was 100%, and the yield of
methyl glycolate was 92%. However, there is still room for further improvement of
the selectivity of methyl glycolate.
Chinese patent application CN105622418A disclosed a method and catalyst
for methyl the preparation of methyl glycolate from oxalate by hydrogenation. The
catalyst used copper as the active component and composite oxide of silicon dioxide
as the carrier. The selectivity of methyl glycolate was high, but the conversion of
oxalate was low.
The Chinese patent application CN107442113A disclosed a multistage nano
flower structure Ag catalyst for the hydrogenation of oxalate to methyl glycolate.
The reaction temperature was 180-220 C, the reaction pressure was 1-4 MPa, the
molar hydrogen ester ratio was 80-120, the mass space velocity of oxalate was 1.5-2
h-', the final conversion of oxalate was 98.6%, and the selectivity of methyl
glycolate was 94.5%. The preparation of catalyst is complex, the synthesis process
of support is difficult to control, the repeatability is poor, the process is not suitable
for industrial production, and the conversion is low.
Chinese patent CN103372453B disclosed a catalyst for the synthesis of methyl glycolate and preparation method thereof. The catalyst was expressed as Ag-M/SiO 2
, wherein SiO2 was the carrier, Ag was the main active component, and M was the
promoter, wherein the mass of Ag accounts for 1%-20% of the total mass of the
catalyst, and the mass of M accounts for 0.1%-5.0% of the total mass of the catalyst.
The promoter M was one or more of Mg, Ca, Ti, Zr, V, Nb, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Au, Zn, Cd, B, Al, C, N, P, La and Ce, but the
preparation method of the catalyst mentioned in the patent was complex and not
easy to be industrialized. The selectivity of methyl glycolate needs to be improved.
Although the patent disclosed that promoters can be added to the catalyst, in fact,
not all of the listed promoters have good effects. In fact, the type and amount of
promoters have a great impact on the catalyst. According to the current reported technology, Cu and Ag catalysts are basically used in the synthesis of methyl glycolate from oxalate by hydrogenation. In the actual preparation and application process, the distribution of active components of the catalyst is uneven, and with the extension of reaction time, Cu and Ag particles are sintered, and then grow up, resulting in the reduction of conversion and selectivity.
SUMMARY OF THE INVENTION The purpose of the invention is to provide a catalyst for producing methyl
glycolate with high activity, high selectivity, simple catalyst preparation and low
cost, and a preparation method and use thereof, to overcome the defects of the prior
art.
The object of the invention can be realized by the following technical solution:
a catalyst for producing methyl glycolate, characterized in that it comprises the
following components in percentage by weight:
silicon dioxide 65%-90%;
silver elements 5%-20%;
nickel elements 0.1-5 %;
lanthanum elements 0.01%-5%;
metal element M 0.01%-5%;
The metal element M is selected from one of titanium, cerium, cobalt or zirconium, and the elements exist in the form of being bound with oxygen. The sum of mass percent content of lanthanum elements and metal element M is more than 0.05% and less than 8%.
A porous silicon dioxide with average particle size of 0.1-6mm and BET specific surface area of 200-600 m2/g is selected as the silicon dioxide. The silver elements, nickel elements, lanthanum elements and metal element M are derived from their corresponding nitrates. A preparation method of a catalyst for producing methyl glycolate, characterized by comprising the following steps: (1) weighing salt solutions of silver, nickel, lanthanum and metal element M to prepare a mixed solution of certain concentration; (2) weighing a certain amount of silicon dioxide according to the composition requirements of the catalyst; (3) pouring the silicon dioxide carrier prepared in step (2) into the mixed solution prepared in step (1); (4) putting the mixture of silicon dioxide and the mixed solution prepared in step (3) into an ultrasonic reactor and treating for 20-60 min; (5) placing the solid and solution after the reaction in step (4) at room temperature for 1-6 h, drying and roasting to obtain the product. In step (5), the drying temperature is 80~100°C, the drying time is 10~24 h, the roasting temperature is 450~550 C, and the roasting time is 2~6 h. Use of a catalyst for producing methyl glycolate, characterized in that the catalyst is used for the reaction of dimethyl oxalate and gas containing molecular hydrogen to produce methyl glycolate. The reaction is carried out at 180-250 C, a molar ratio of hydrogen to dimethyl oxalate of (40-200):1, a reaction pressure of 2.0-3.5 MPa and a space velocity of 0.1-2.0 h'. Compared with the prior art, through the ultrasonic reaction of the mixed silicon dioxide and solution, the invention can significantly increase the dispersion of each element, and load each element on the catalyst more evenly. The addition of lanthanum and zirconium elements can significantly improve the aggregation of silver elements on the catalyst and the thermal stability of the catalyst. The addition of lanthanum elements also leads to a significant increase in the surface active sites of the catalyst, and there is no continuous increase of silver particles in the later use process. Therefore, the invention is used for the hydrogenation of oxalate to produce methyl glycolate, which has better activity and selectivity of methyl glycolate, better thermal stability, simpler preparation method and lower cost than existing catalysts.
DETAILED DESCRIPTION OF THE INVENTION The following is a detailed description of the embodiments of the invention. The embodiments are implemented on the premise of the technical solution of the invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the invention is not limited to the following embodiments. Example 1 110 g deionized water was added to 12.75 g silver nitrate, 5.01 g nickel nitrate, 0.35 g lanthanum nitrate and 0.52 g zirconium nitrate to prepare solution I. 100 g silicon dioxide was added to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor and reacted for 40 minutes, then it was taken out and soaked at room temperature for 2 hours. Then it was dried at 80 °C for 12 hours and roasted at 500 °C for 4 hours. Catalyst MG-1 for the production of methyl glycolate was obtained after roasting. The sample was tested by ICP. The results are shown in Table 1. Example 2 110 g deionized water was added to 12.75 g silver nitrate, 7.71 g nickel nitrate, 0.35 g lanthanum nitrate and 0.52 g zirconium nitrate to prepare solution I. 100 g silicon dioxide was added to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor and reacted for 40 minutes, then it was taken out and soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours and roasted at 500 C for 4 hours. Catalyst MG-2 for the production of methyl glycolate was obtained after roasting. The sample was tested by ICP. The results are shown in Table 1. Example 3 110 g deionized water was added to 12.75 g silver nitrate, 10.24 g nickel nitrate, 0.35 g lanthanum nitrate and 0.52 g zirconium nitrate to prepare solution I. 100 g silicon dioxide was added to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor and reacted for 40 minutes, then it was taken out and soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours and roasted at 500 C for 4 hours. Catalyst MG-3 for the production of methyl glycolate was obtained after roasting. The sample was tested by ICP. The results are shown in Table 1. Example 4 110 g deionized water was added to 24.33 g silver nitrate, 5.01 g nickel nitrate, 1.12 g lanthanum nitrate and 1.18 g zirconium nitrate to prepare solution I. 100 g silicon dioxide was added to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor and reacted for 50 minutes, then it was taken out and soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours and roasted at 500 C for 4 hours. Catalyst MG-4 for the production of methyl glycolate was obtained after roasting. The sample was tested by ICP. The results are shown in Table 1. Example 5 110 g deionized water was added to 24.33 g silver nitrate, 5.01 g nickel nitrate, 1.73 g lanthanum nitrate and 1.18 g zirconium nitrate to prepare solution I. 100 g silicon dioxide was added to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor and reacted for 50 minutes, then it was taken out and soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours and roasted at 500 C for 4 hours. Catalyst MG-5 for the production of methyl glycolate was obtained after roasting. The sample was tested by ICP. The results are shown in Table 1.
Example 6
110 g deionized water was added to 24.33 g silver nitrate, 5.01 g nickel nitrate, 1.12 g lanthanum nitrate and 0.28 g zirconium nitrate to prepare solution I. 100 g
silicon dioxide was added to solution I to prepare mixture II. The mixture II was put
into an ultrasonic reactor and reacted for 50 minutes, then it was taken out and
soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours
and roasted at 500 C for 4 hours. Catalyst MG-6 for the production of methyl
glycolate was obtained after roasting. The sample was tested by ICP. The results are
shown in Table 1.
Example 7
110 g deionized water was added to 24.33 g silver nitrate, 5.01 g nickel nitrate,
1.12 g lanthanum nitrate and 0.81 g zirconium nitrate to prepare solution I. 100 g
silicon dioxide was added to solution I to prepare mixture II. The mixture II was put
into an ultrasonic reactor and reacted for 50 minutes, then it was taken out and
soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours
and roasted at 500 C for 4 hours. Catalyst MG-7 for the production of methyl
glycolate was obtained after roasting. The sample was tested by ICP. The results are
shown in Table 1.
Example 8
110 g deionized water was added to 14.77 g silver nitrate, 7.62 g nickel nitrate,
1.12 g lanthanum nitrate and 2.50 g cobalt nitrate to prepare solution I. 100 g
silicon dioxide was added to solution I to prepare mixture II. The mixture II was put
into an ultrasonic reactor and reacted for 50 minutes, then it was taken out and
soaked at room temperature for 2 hours. Then it was dried at 80 C for 12 hours
and roasted at 500 C for 4 hours. Catalyst MG-8 for the production of methyl
glycolate was obtained after roasting. The sample was tested by ICP. The results are shown in Table 1.
Comparative example 1
110 g deionized water was added to 12.75 g silver nitrate, 7.71 g nickel nitrate,
0.35 g lanthanum nitrate and 0.52 g zirconium nitrate to prepare solution I. 100 g
silicon dioxide was added to solution I to prepare mixture II. The mixture II was
soaked at room temperature for 2 hours Then it was dried at 80 C for 12 hours
and roasted at 500 C for 4 hours. Catalyst MG-9 for the production of methyl
glycolate was obtained after roasting. The sample was tested by ICP. The results are
shown in Table 1.
Comparative example 2
110 g deionized water was added to 24.33 g silver nitrate, 5.01 g nickel nitrate
and 0.28 g zirconium nitrate to prepare solution I. 100 g silicon dioxide was added
to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor
and reacted for 50 minutes, then it was taken out and soaked at room temperature
for 2 hours. Then it was dried at 80 C for 12 hours and roasted at 500 C for 4
hours. Catalyst MG-10 for the production of methyl glycolate was obtained after
roasting. The sample was tested by ICP. The results are shown in Table 1.
Comparative example 3
110 g deionized water was added to 24.33 g silver nitrate, 5.01 g nickel nitrate
and 1.12 g lanthanum nitrate to prepare solution I. 100 g silicon dioxide was added
to solution I to prepare mixture II. The mixture II was put into an ultrasonic reactor
and reacted for 50 minutes, then it was taken out and soaked at room temperature
for 2 hours. Then it was dried at 80 C for 12 hours and roasted at 500 C for 4
hours. Catalyst MG-11 for the production of methyl glycolate was obtained after
roasting. The sample was tested by ICP. The results are shown in Table 1.
Table 1. ICP Test Results
Catalyst Silver content Contents of other elements
MG-1 7.98% 0.96%Ni-0.1 %La-0.1 %Zr
MG-2 7.98% 1.46%Ni-0.1 %La-0.1 %Zr
MG-3 7.98% 1.92%Ni-0.1 %La-0.1 %Zr
MG-4 14.97% 0.96%Ni-0.27%La-0.180%Zr
MG-5 14.97% 0.96%Ni-0.42%La-0.180%Zr
MG-6 14.97% 0.96%Ni-0.27%La-0.05%Zr
MG-7 14.97% 0.96%Ni-0.27%La-0.150%Zr
MG-8 8.37% 1.46%Ni-0.27%La-0.45%Zr
MG-9 7.98% 1.46%Ni-0.1 %La-0.1 %Zr
MG-10 14.97% 0.96%Ni-0.05%Zr
MG-11 14.97% 0.96%Ni-0.27%La
The catalysts were put into a fixed bed reactor for evaluation test. Dimethyl
oxalate and hydrogen were used as raw materials, the molar ratio of hydrogen and
dimethyl oxalate was 100:1, the reaction temperature was 190 C, the pressure was
2.5 MPa, and the reaction mass space velocity was 1.0 h-'. The reaction results are
shown in Table 2.
Table 2. Reaction Results
Fresh catalyst Catalyst after 72 h reaction
Conversion Conversion Catalyst Selectivity of Selectivity of rateof rateof methyl methyl dimethyl dimethyl glycolate glycolate oxalate oxalate
MG-1 95.27% 85.32% 95.22% 85.31%
MG-2 96.66% 92.51% 96.60% 92.01%
MG-3 96.41% 89.75% 96.41% 89.56%
MG-4 99.98% 95.01% 99.98% 94.78%
MG-5 97.02% 93.16% 96.89% 92.79%
MG-6 100% 98.89% 100% 98.89%
MG-7 99.52% 93.11% 99.37% 92.98%
MG-8 98.05% 96.55% 97.95% 96.50%
MG-9 89.62% 90.34% 70.62% 81.45%
MG-10 95.36% 82.33% 76.62% 69.98%
MG-11 98.17% 83.33% 77.37% 70.38%
It can be seen from the above table that under the action of the catalyst of the
invention, the conversion rate of dimethyl oxalate can reach 100%, and the
selectivity can reach 98.89%. After 72 hours of reaction, the conversion rate of
dimethyl oxalate under the action of the catalyst of the invention has been
maintained at 100%, so the catalyst of the invention has high conversion rate, high selectivity, good dispersion and good thermal stability.
Claims (8)
- What is Claimed: 1. A catalyst for producing methyl glycolate comprising the following components in percentage by weight: silicon dioxide 65%-90%;
- silver elements 5%-20%;
- nickel elements 0.1-5%; lanthanum elements 0.01%-5%; metal element M 0.01%-5%; the metal element M is selected from one of titanium, cerium, cobalt or zirconium, and the elements exist in the form of being bound with oxygen. 2. The catalyst for producing methyl glycolate of claim 1, wherein the sum of mass percent content of lanthanum elements and metal element M is more than 0.05% and less than 8%. 3. The catalyst for producing methyl glycolate of claim 1, wherein a porous silicon dioxide with average particle size of 0.1-6 mm and BET specific surface area of 200-600 m2 /g is selected as the silicon dioxide. 4. The catalyst for producing methyl glycolate of claim 1, wherein the silver elements, nickel elements, lanthanum elements and metal element M are derived from their corresponding nitrates 5. A preparation method of the catalyst for producing methyl glycolate of any one of claims 1~4, comprising the following steps: (1) weighing salt solutions of silver, nickel, lanthanum and metal element M to prepare a mixed solution of certain concentration; (2) weighing a certain amount of silicon dioxide according to the composition requirements of the catalyst; (3) pouring the silicon dioxide carrier prepared in step (2) into the mixed solution prepared in step (1); (4) putting the mixture of silicon dioxide and mixed solution prepared in step (3) into an ultrasonic reactor and treating for 20-60 min;
- (5) placing the solid and solution after the reaction in step (4) at room
- temperature for 1-6 h, drying and roasting to obtain the product.
- 6. The preparation method of the catalyst for producing methyl glycolate ofclaim 6, wherein in step (5), the drying temperature is 80~100 °C, the drying time is 10~24 h, the roasting temperature is 450~550 °C, and the roasting time is 2~6 h.
- 7. Use of the catalyst for producing methyl glycolate of claim 1, wherein thecatalyst is used for the reaction of dimethyl oxalate and gas containing molecularhydrogen to produce methyl glycolate.
- 8. Use of the catalyst for producing methyl glycolate of claim 7, wherein thereaction is carried out at 180-250 °C, a molar ratio of hydrogen to dimethyl oxalateof (40-200):1, a reaction pressure of 2.0-3.5 MPa and a space velocity of 0.1-2.0 h-'.
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CN201810961927.XA CN110856817B (en) | 2018-08-22 | 2018-08-22 | Catalyst for producing methyl glycolate and preparation method and application thereof |
PCT/CN2019/101924 WO2020038428A1 (en) | 2018-08-22 | 2019-08-22 | Catalyst used for producing methyl glycolate and preparation method and application thereof |
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CN111495373B (en) * | 2020-04-22 | 2023-03-10 | 陕西延长石油(集团)有限责任公司 | Catalyst and method for preparing glycine methyl ester and glycine from methyl glycolate by using double-metal glass wire layered eutectic |
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US8105971B2 (en) * | 2009-04-02 | 2012-01-31 | Lummus Technology Inc. | Process for making catalysts useful for the conversion of paraffins to olefins |
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