Application method of catalyst extrusion molding process binder
In the extrusion process of the catalyst preparation of ethylene glycol, the adhesive is added in an appropriate amount and the reaction conditions are controlled to prepare an improved catalyst, which solves the problem of the inappropriate addition of binder in the prior art, resulting in the reduction of catalyst activity and selectivity, and improves the catalyst strength and reaction efficiency.
Patent Information
- Application Number
- CN202411860958.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-17
- Publication Date
- 2025-04-04
AI Technical Summary
The existing catalyst for preparation of ethylene glycol is not suitable for the type and method of adding binder, resulting in a decrease in activity and selectivity of the catalyst.
An improved catalyst is prepared by applying a catalyst extrusion process by adding the binder to the catalyst powder, mixing it evenly, and then drying and calculating the amount of binder and reaction conditions.
The strength and pore size after catalyst molding are improved, the reaction speed of reaction products and heat in the catalyst is enhanced, the activity and selectivity of the catalyst is maintained, and the problem of decrease in activity and selectivity caused by inappropriate addition of binder is solved.
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Figure CN119746949A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of ethylene glycol preparation catalyst, in particular to an application method of a catalyst extrusion molding process binder. Background Art
[0002] The reaction of dimethyl oxalate with hydrogen to produce ethylene glycol usually adopts a fixed bed tubular reactor, and the main active ingredient of the catalyst is metallic copper. The current mainstream molding methods are extrusion and tableting, and both methods have their own advantages and disadvantages. The main problem with the tableting process is that the system pressure difference rises relatively quickly. Once the device is shut down in an emergency, the pressure difference rises quickly when the catalyst is used again, causing a decrease in the system circulation volume and an increase in hot spots, which requires the catalyst to be replaced. Extruded catalysts have certain advantages in terms of pressure difference, but there are problems with reduced catalyst activity and selectivity due to the type of binder added and the different methods of addition.
[0003] Therefore, the extrusion molding process should select an appropriate amount of binder addition, and the drying operation after extrusion molding should also be considered. The higher the content of the binder, the greater the shrinkage rate after drying. Excessive drying temperature can also easily cause sample cracking. To this end, the applicant proposes an application method of a binder in a catalyst extrusion molding process. Summary of the invention
[0004] The purpose of the present invention is to provide an application method of a binder in a catalyst extrusion molding process to solve the problem that the catalyst activity and selectivity of the existing catalyst for ethylene glycol preparation are reduced due to inappropriate type and method of adding the binder.
[0005] The present invention is achieved in that:
[0006] The present invention provides an application method of a catalyst extrusion molding process binder, comprising the following steps:
[0007] S100, adding a binder to the catalyst powder and mixing them evenly to obtain a mixture of the binder and the catalyst;
[0008] S200, drying the uniformly mixed mixture;
[0009] S300, calcining the dried mixture;
[0010] S400, sending the calcined mixture into an extruder for compression, extrusion and strip cutting to obtain an improved catalyst.
[0011] Furthermore, in step S100, the binder is one or more of sesbania powder, starch thickener, cellulose, and phosphoric acid.
[0012] Furthermore, the weight percentage of each component in the mixture is: binder: 1-10 w t%, catalyst powder=90-99wt%.
[0013] Furthermore, in the step S200, the uniformly mixed mixture is dried in an oven at 80-120°C for 12 hours.
[0014] Furthermore, in step S300, the dried mixture is calcined at 450-550°C for 3h.
[0015] The present invention also provides a method for preparing ethylene glycol, which uses the improved catalyst prepared by the above application method to prepare ethylene glycol.
[0016] Furthermore, in a fixed bed reactor, dimethyl oxalate, hydrogen and the improved catalyst are placed in the fixed bed reactor, and reduced using 5% H2 / N2, the reduction temperature is 180-220°C, and the reduction time is 2-24 hours; after the reduction is completed, ethylene glycol is generated at a temperature of 150-200°C and a pressure of 1-3MPa. The hydrogen-to-ester ratio is 60-150, the liquid hourly space velocity is 0.2-1.0, the ethylene glycol selectivity is above 97%, and the activity is above 99.5%.
[0017] Experiments show that the binder selected in the present invention not only has no effect on the activity and selectivity of the catalyst, but also improves the strength of the catalyst to a certain extent.
[0018] The technical solution adopted in the present invention effectively improves the strength and pore size of the catalyst after molding by controlling the type, ratio and reaction conditions of the binder added, increases the reaction rate of the reaction products and heat in the catalyst, and reduces the impact on the selectivity and activity of the catalyst.
[0019] Compared with the prior art, the present invention has the following beneficial effects: the improved catalyst prepared by the present invention not only has high strength after molding, but also does not reduce the activity and selectivity of the catalyst, thereby solving the problem that the activity and selectivity of the existing catalyst for ethylene glycol preparation are reduced due to inappropriate types and methods of binder addition. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 This is a comparison table of catalyst performance evaluation results. DETAILED DESCRIPTION
[0021] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0022] Example 1: (1% sesbania powder-catalyst powder-2% starch thickener)
[0023] Improved catalyst preparation
[0024] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0025] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of sesbania powder, and starting the mixer to mix for 30 minutes for later use;
[0026] 3) Weigh 5 g of starch thickener and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0027] 4) drying the catalyst powder prepared in step 3) in an oven at 110° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining at 550° C. for 3 h;
[0028] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0029] Catalyst evaluation
[0030] The reaction is carried out in a fixed bed reactor. The prepared catalyst is molded and placed in a fixed bed reactor. It is reduced using 5% H2 / N2 at a reduction temperature of 180-220°C for 2-24 hours. After the reduction is completed, the temperature is controlled to 150-200°C and the pressure is 1-3MPa. Ethylene glycol is generated by the reaction, the hydrogen-ester ratio is 60-150, and the liquid hourly space velocity is 0.2-1.0h-1. The results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0031] Example 2: (1% sesbania powder-catalyst powder-5% starch thickener)
[0032] Improved catalyst preparation
[0033] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0034] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of sesbania powder, and starting the mixer to mix for 30 minutes for later use;
[0035] 3) Weigh 12.5 g of starch thickener and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0036] 4) drying the catalyst powder prepared in step 3) in an oven at 110° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining at 550° C. for 3 h;
[0037] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0038] Catalyst evaluation
[0039] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0040] Example 3: (1% cellulose-catalyst powder-2% starch thickener)
[0041] Improved catalyst preparation
[0042] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0043] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of cellulose, and starting the mixer to mix for 30 minutes for later use;
[0044] 3) Weigh 5 g of starch thickener and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0045] 4) drying the catalyst powder prepared in step 3) in an oven at 110° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining at 550° C. for 3 h;
[0046] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0047] Catalyst evaluation
[0048] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0049] Example 4: (1% sesbania powder-catalyst powder-2% phosphoric acid)
[0050] Improved catalyst preparation
[0051] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0052] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of sesbania powder, and starting the mixer to mix for 30 minutes for later use;
[0053] 3) Weigh 5 g of phosphoric acid and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0054] 4) drying the catalyst powder prepared in step 3) in an oven at 110° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining at 550° C. for 3 h;
[0055] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0056] Catalyst evaluation
[0057] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0058] Example 5: (2% sesbania powder-catalyst powder-2% phosphoric acid)
[0059] Improved catalyst preparation
[0060] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0061] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 5 g of sesbania powder, and starting the mixer to mix for 30 minutes for later use;
[0062] 3) Weigh 5 g of phosphoric acid and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0063] 4) drying the catalyst powder prepared in step 3) in an oven at 110° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining at 550° C. for 3 h;
[0064] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0065] Catalyst evaluation
[0066] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0067] Example 6: (1% sesbania powder-catalyst powder-2% starch thickener)
[0068] Improved catalyst preparation
[0069] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0070] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of sesbania powder, and starting the mixer to mix for 30 minutes for later use;
[0071] 3) Weigh 5 g of starch thickener and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0072] 4) drying the catalyst powder prepared in step 3) in an oven at 100° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining it at 500° C. for 3 h;
[0073] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0074] Catalyst evaluation
[0075] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0076] Example 7: (1% sesbania powder-catalyst powder-5% starch thickener)
[0077] Improved catalyst preparation
[0078] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0079] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of sesbania powder, and starting the mixer to mix for 30 minutes for later use;
[0080] 3) Weigh 12.5 g of starch thickener and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0081] 4) drying the catalyst powder prepared in step 3) in an oven at 100° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining it at 500° C. for 3 h;
[0082] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0083] Catalyst evaluation
[0084] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0085] Example 8: (1% cellulose-catalyst powder-2% starch thickener)
[0086] Improved catalyst preparation
[0087] 1) Weigh 250g of catalyst powder and evenly spray 250g of desalted water to mix well;
[0088] 2) putting the catalyst powder mixed evenly in step 1) into a mixer, adding 2.5 g of cellulose, and starting the mixer to mix for 30 minutes for later use;
[0089] 3) Weigh 5 g of starch thickener and add it to the powder prepared in step 2), start the mixer and mix for 30 minutes;
[0090] 4) drying the catalyst powder prepared in step 3) in an oven at 120° C. for 12 h, and transferring the dried catalyst to a muffle furnace and calcining at 550° C. for 3 h;
[0091] 5) The calcined powder is sent to an extruder for compression, extrusion and cutting.
[0092] The catalyst evaluation method is the same as in Example 1, and the results are shown in Figure 1 The comparison table of catalyst performance evaluation results is shown.
[0093] By comparing Examples 1 and 2, it can be seen that the amount of starch thickener added should not be too much, and the amount of binder added should exceed a certain ratio. The more binder is added, the greater the shrinkage after drying, which causes changes in the pore size of the catalyst and affects the activity and selectivity.
[0094] By comparing Examples 1 and 3, it can be seen that the addition of cellulose will affect the activity and selectivity of the catalyst.
[0095] By comparing Examples 1, 4 and 5, it can be seen that when the content of sesbania powder is below 2%, it has little effect on the catalyst performance, but the addition of phosphoric acid leads to a significant decrease in the catalyst activity and selectivity.
[0096] Comparison of 1, 6, and 7 shows that the drying and calcination temperatures have a certain influence on the performance of the catalyst. If the drying temperature is too high, the water evaporates quickly, which can easily lead to cracking of the catalyst sample, thereby reducing the strength of the catalyst and affecting the activity and selectivity of the catalyst.
[0097] from Figure 1 It can be seen from the comparison table of catalyst performance evaluation results that when the raw material for the extrusion molding process is powder, it is necessary to add an appropriate binder to the raw material for kneading and molding. The amount of binder added is closely related to the particle state of the raw material. In addition, the ratio of the binder and the drying and calcining temperature after extrusion also have a certain impact on the performance of the catalyst. The improved catalyst prepared by the patent of the present invention not only has high strength after molding, but also does not reduce the activity and selectivity of the catalyst, which solves the problem that the catalyst activity and selectivity of the existing catalyst for ethylene glycol preparation are reduced due to the inappropriate type and method of adding binders.
[0098] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for applying a binder in a catalyst extrusion molding process, characterized in that: The following steps are involved: S100, adding a binder to the catalyst powder and mixing them evenly to obtain a mixture of the binder and the catalyst; S200, drying the uniformly mixed mixture; S300, calcining the dried mixture; S400, sending the calcined mixture into an extruder for compression, extrusion and strip cutting to obtain an improved catalyst.
2. The application method of the catalyst extrusion molding process binder according to claim 1, characterized in that: In the step S100, the binder is one or more of sesbania powder, starch thickener, cellulose, and phosphoric acid.
3. The application method of the catalyst extrusion molding process binder according to claim 2, characterized in that: The weight percentage of each component in the mixture is: binder: 1-10wt%, catalyst powder = 90-99wt%.
4. The application method of the catalyst extrusion molding process binder according to claim 1, characterized in that: In the step S200, the uniformly mixed mixture is dried in an oven at 80-120°C for 12 hours.
5. The application method of the catalyst extrusion molding process binder according to claim 1, characterized in that: In the step S300, the dried mixture is calcined at 450-550°C for 3 hours.
6. A method for preparing ethylene glycol, characterized in that: The improved catalyst prepared by the application method according to any one of claims 1 to 5 is used to prepare ethylene glycol.
7. The method for preparing ethylene glycol according to claim 6, characterized in that: The process is carried out in a fixed bed reactor. Dimethyl oxalate, hydrogen and an improved catalyst are placed in the fixed bed reactor and reduced using 5% H2 / N2 at a reduction temperature of 180-220°C for a reduction time of 2-24 hours. After the reduction is completed, ethylene glycol is generated by reaction at a temperature of 150-200°C and a pressure of 1-3MPa.