Methanol waste liquid recovery and treatment device for BDO (Butyl Dissolved Oxygen) process by

Abstract

The utility model belongs to the fields of chemical engineering, fuel preparation and waste material recycling, and particularly relates to a device for recycling methanol waste liquid in an alkyne-aldehyde method BDO (Butyl Dissolved Oxygen) process. The recovery treatment device comprises a dehydrating tower connected with a methanol waste liquid outlet of the alkyne-aldehyde method BDO production device, conveying equipment connected with a tower top outlet of the dehydrating tower, and a methanol decoloration reactor connected with the conveying equipment. The recovery treatment device disclosed by the utility model is low in equipment investment, low in energy consumption and good in economic benefit. The recovery treatment device is directly connected with the methanol waste liquid outlet of an alkyne-aldehyde method BDO production device, the methanol waste liquid from an alkyne-aldehyde method BDO process can be converted into the alcohol-based fuel through rectification and hydrogenation reaction when the recovery treatment device is used for treating the methanol waste liquid, the treated alcohol-based fuel meets the index requirements of GB16663 alcohol-based fuel, and the methanol waste liquid can be recycled. The economic value of the methanol waste liquid is effectively improved.

Description

Technical Field

[0001] The utility model belongs to the fields of chemical engineering, fuel preparation and waste resource utilization, and specifically relates to a methanol waste liquid recovery and treatment device of an acetylene-aldehyde method BDO process. Background Art

[0002] In the field of chemical engineering, especially in the production process of 1, 4-butanediol (BDO) by the acetylene aldehyde method, a large amount of methanol waste liquid is generated. These methanol waste liquids mainly contain components such as methanol, formaldehyde, propargyl alcohol, ethanol and water. Methanol is an important industrial raw material and fuel with a wide range of application value. However, since methanol waste liquid contains other impurities, its economic value is limited and it is usually treated as waste. In the field of fuel preparation, alcohol-based fuel is an important clean fuel with the advantages of high combustion efficiency and low pollutant emissions. The main component of alcohol-based fuel is methanol, but it can also contain other alcohols and a small amount of impurities. In the field of waste resource utilization, how to effectively recycle and utilize waste in industrial processes is an important research direction. As a potential resource, methanol waste liquid, if it can be effectively utilized, can not only reduce environmental pollution, but also reduce the cost of industrial production. However, the existing methanol waste liquid treatment methods cannot meet the index requirements of alcohol-based fuels.

[0003] Existing methods for treating methanol waste liquid mainly include incineration treatment, hazardous waste treatment and distillation recovery. Incineration treatment is to burn methanol waste liquid and convert it into heat energy or electrical energy. Although this method can reduce the volume and weight of methanol waste liquid, it will produce a large amount of carbon dioxide and other harmful gases, causing secondary environmental pollution. Hazardous waste treatment is to treat methanol waste liquid as hazardous waste, which not only wastes resources, but also increases the environmental pressure of enterprises. In addition, there are also some technical attempts to recover methanol in methanol waste liquid by distillation to improve its economic value. For example, CN212594065U and CN204803244U adopt a method of combining filtration with distillation, first removing solid impurities in methanol waste liquid through a specific filtering mechanism, and then distilling. CN216395301U first treats methanol waste liquid through distillation and then through a filter.

[0004] There are some problems and shortcomings in the existing method for treating methanol waste liquid. First, since the main component of methanol waste liquid is methanol, low-cost treatment is a waste. Secondly, simple incineration treatment will lead to the discharge of wastewater and waste gas, and the harmful substances therein will cause secondary environmental pollution. Thirdly, although the concentration of methanol can be increased by distillation, it is necessary to increase the height of the packing and achieve it through a large reflux rate, which leads to a significant increase in equipment investment and energy consumption, and is not economically feasible. In addition, the impurities separated from the tower still need to be discharged, and the environmental protection problem cannot be completely solved. Therefore, how to effectively recycle and utilize methanol waste liquid, improve its economic value, and reduce environmental pollution at the same time is an important problem facing the current technology. Utility Model Content

[0005] In view of the problems existing in the prior art, the utility model provides a methanol waste liquid recovery and treatment device in an acetylene-aldehyde method BDO process.

[0006] Specifically, the recovery and processing device of the utility model includes a dehydration tower connected to the methanol waste liquid outlet of the acetylene aldehyde method 1,4-butanediol production device, a conveying device connected to the top outlet of the dehydration tower, and a methanol decolorization reactor connected to the conveying device.

[0007] In one or more embodiments, the transporting equipment includes a top condenser connected to the top outlet of the dehydration tower, and a distillation pump connected to the top condenser, wherein the distillation pump is used to pump a portion of the liquid cooled in the top condenser into the methanol decolorization reactor and the remaining portion into the dehydration tower.

[0008] In one or more embodiments, a distillation tank is further provided between the top condenser and the distillation pump.

[0009] In one or more embodiments, the methanol decolorization reactor is a hydrogenation reactor.

[0010] In one or more embodiments, a gas inlet is disposed at the top of the methanol decolorization reactor.

[0011] In one or more embodiments, a discharge port is disposed at the bottom of the methanol decolorization reactor.

[0012] In one or more embodiments, a gas outlet is disposed on the side wall of the methanol decolorization reactor, and the gas outlet is close to the discharge port.

[0013] In one or more embodiments, the recovery and processing device further comprises a methanol filter connected to the discharge port of the methanol decolorization reactor.

[0014] In one or more embodiments, the recovery and processing device further comprises a vapor-liquid separation tank connected to the discharge port of the methanol filter.

[0015] In one or more embodiments, the recovery and processing device further comprises a tail gas condenser connected to the gas outlet of the vapor-liquid separation tank.

[0016] In one or more embodiments, the recovery treatment device further comprises a reboiler connected to the bottom outlet of the dehydration tower.

[0017] In one or more embodiments, the recovery processing device further comprises a bottom pump connected to the bottom outlet of the dehydration tower.

[0018] In one or more embodiments, the dehydration column is a distillation column.

[0019] In one or more embodiments, the dehydration tower uses fixed valve trays.

[0020] Compared with the existing technology, the utility model has the following beneficial effects:

[0021] 1. The recycling and processing device of the utility model has low equipment investment, low energy consumption and good economic benefits.

[0022] 2. The process flow of treating methanol waste liquid by the utility model recovery and treatment device is simple, and there is no need to increase the packing height or to achieve distillation through a large reflux flow, which greatly reduces equipment investment and energy consumption.

[0023] 3. The utility model recovery and treatment device is directly connected to the methanol waste liquid outlet of the acetylene-aldehyde method BDO process. The utility model recovery and treatment device is used to treat the methanol waste liquid, and the methanol waste liquid from the acetylene-aldehyde method BDO process can be converted into alcohol-based fuel through distillation and hydrogenation reaction. The treated alcohol-based fuel meets the index requirements of GB16663 alcohol-based fuel, and effectively improves the economic value of the methanol waste liquid. The process of using the utility model recovery and treatment device to treat the methanol waste liquid can not only avoid the low-cost treatment of the methanol waste liquid, but also reduce environmental pollution, and has good environmental benefits.

[0024] 4. The utility model recovery and processing device is provided with a methanol filter, which can filter out the catalyst powder, thereby ensuring the purity and quality of the product.

[0025] In general, the utility model provides a new methanol waste liquid treatment device, which can not only effectively recycle and utilize methanol waste liquid and improve its economic value, but also reduce environmental pollution, and has good environmental and economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1It is a schematic diagram of a recycling and processing device in one or more embodiments of the utility model.

[0027] Explanation of the reference numerals: 1-dehydration tower; 2-methanol decolorization reactor; 3-distillation tank; 4-vapor-liquid separation tank; 5-tower top condenser; 6-reboiler; 7-tail gas condenser; 8-distillation pump; 9-tower bottom pump; 10-methanol filter; STM-water vapor; CHW-cooling water. DETAILED DESCRIPTION

[0028] In order to enable those skilled in the art to understand the features and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in this document. Unless otherwise specified, all technical and scientific terms used in this document have the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definitions in this specification shall prevail.

[0029] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0030] Herein, “comprising”, “including”, “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of”. For example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to be disclosed herein.

[0031] In this document, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible sub-ranges and individual values ​​within the range (including integers and fractions).

[0032] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0033] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope defined by the present invention.

[0034] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0035] like Figure 1 As shown, the utility model provides a recovery and treatment device, which includes a dehydration tower 1 connected to the methanol waste liquid outlet of the 1,4-butanediol production device, a conveying device connected to the tower top outlet of the dehydration tower 1, and a methanol decolorization reactor 2 connected to the conveying device. The recovery and treatment device of the utility model can be used to treat the methanol waste liquid of the acetylene aldehyde method BDO production process. First, the methanol waste liquid is passed into the dehydration tower 1 to concentrate the methanol waste liquid and separate most of the aldehyde compounds; then it enters the methanol decolorization reactor 2 for decolorization to eliminate the pungent odor contained in the methanol waste liquid and solve the color problem, thereby improving the economic value of the methanol waste liquid.

[0036] The dehydration tower 1 of the utility model is a distillation tower. Preferably, the dehydration tower 1 adopts a fixed valve tower plate. Furthermore, the recovery and processing device also includes a reboiler 6 connected to the bottom outlet of the dehydration tower 1, and part of the bottom liquid containing impurities enters the reboiler 6, is heated by water vapor (STM), and then circulates into the dehydration tower 1 for distillation. Furthermore, the recovery and processing device also includes a bottom pump 9 connected to the bottom outlet of the dehydration tower 1. Part of the bottom liquid containing impurities leaves the recovery and processing device of the utility model and is transported to other processing units by the bottom pump 9. For example, part of the bottom liquid is sent to other devices for reuse or incineration, so as to realize the reuse of resources and further improve economic benefits.

[0037] The utility model does not limit the decolorization method in the methanol decolorization reactor 2, and conventional decolorization methods in the art can be used, such as adsorption, hydrogenation, etc. In some embodiments, the methanol decolorization reactor 2 of the utility model is a hydrogenation reactor. The top of the methanol decolorization reactor 2 is provided with an air inlet, which can be used for hydrogen intake. The bottom of the methanol decolorization reactor 2 is provided with a discharge port, which can be used to discharge alcohol-based fuel. Preferably, a gas outlet is also provided on the side wall of the methanol decolorization reactor 2, and the gas outlet is close to the discharge port, and the gas outlet is used to discharge incomplete hydrogen. In the methanol decolorization reactor 2, the hydrogenation reaction can remove aldehydes and coloring functional groups in the methanol waste liquid under the action of a nickel-based catalyst, eliminate the pungent odor and chromaticity problems of the methanol waste liquid, and improve the quality of the product.

[0038] The conveying equipment can be used to convey the liquid phase or the vapor phase. In some embodiments, the conveying equipment includes a top condenser 5 connected to the top outlet of the dehydration tower 1, and a distillation pump 8 connected to the top condenser 5. The distillation pump 8 is used to pump a portion of the liquid cooled in the top condenser 5 into the methanol decolorization reactor 2 and the remaining portion into the dehydration tower 1. Preferably, a distillation tank 3 is also provided between the top condenser 5 and the distillation pump 8.

[0039] In practical applications, the methanol waste liquid flowing out of the methanol waste liquid outlet of the acetylene aldehyde process BDO production process device enters the dehydration tower 1, and the methanol waste liquid is distilled in the dehydration tower 1. The main components of the top vapor phase are methanol, water, propargyl alcohol, etc., and the main components of the bottom liquid are water, a small amount of methanol waste liquid and aldehydes, etc. The top vapor phase enters the top condenser 5 for condensation, and the condensate enters the distillation tank 3, further flows out from the outlet of the distillation tank 3, and is pumped into the dehydration tower 1 and the methanol decolorization reactor 2 by the distillation pump 8, that is, the concentrated methanol waste liquid obtained after the top vapor phase is condensed is partially entered into the methanol decolorization reactor 2 for decolorization, and partially returned to the dehydration tower 1 for distillation.

[0040] Furthermore, the recovery and processing device of the utility model further comprises a methanol filter 10 connected to the discharge port of the methanol decolorization reactor 2. The alcohol-based fuel flowing out of the discharge port of the methanol decolorization reactor 2 may carry catalyst powder in the methanol decolorization reactor 2, and the methanol filter 10 can filter out the catalyst powder carried in the alcohol-based fuel.

[0041] Furthermore, the recovery and processing device also includes a vapor-liquid separation tank 4 connected to the discharge port of the methanol filter 10. The alcohol-based fuel flowing out of the discharge port of the methanol filter 10 may carry dissolved hydrogen, and passing it into the vapor-liquid separation tank 4 can separate the hydrogen by flash evaporation. Preferably, the gas outlet of the methanol decolorization reactor 2 is connected to the vapor-liquid separation tank 4. The gas outlet of the methanol decolorization reactor 2 discharges unreacted hydrogen carrying alcohol-based fuel, and passes it into the vapor-liquid separation tank 4 for vapor-liquid separation.

[0042] In practical applications, the bottom liquid phase of the methanol decolorization reactor 2 is an alcohol-based fuel entrained with hydrogen, and the gas outlet of the methanol decolorization reactor 2 flows out hydrogen entrained with the alcohol-based fuel. The bottom liquid phase of the methanol decolorization reactor 2 enters the methanol filter 10 to filter out the catalyst, and the alcohol-based fuel discharged from the discharge port of the methanol filter 10 may still be entrained with hydrogen. Therefore, the liquid phase discharged from the discharge port of the methanol filter 10 and the gas discharged from the gas outlet of the methanol decolorization reactor 2 both enter the vapor-liquid separation tank 4 for vapor-liquid separation. The top gas outlet of the vapor-liquid separation tank 4 discharges unreacted hydrogen, and the bottom discharge port of the vapor-liquid separation tank 4 discharges alcohol-based fuel that meets the requirements of the GB16663 alcohol-based fuel index.

[0043] Furthermore, the recovery and processing device also includes a tail gas condenser 7 connected to the gas outlet of the vapor-liquid separation tank 4. The hydrogen discharged from the top gas outlet of the vapor-liquid separation tank 4 may still contain vaporized alcohol-based fuel, and the gas is passed into the tail gas condenser 7 for cooling. The entrained alcohol-based fuel can be liquefied under the cooling effect of cooling water (CHW) and circulated back to the vapor-liquid separation tank 4 through the pipeline, and the uncooled gas in the tail gas condenser 7 is discharged from the recovery and processing device of the utility model.

[0044] In the field of chemical engineering, the utility model provides a simple and convenient recovery and processing device, which can be used to convert methanol waste liquid into alcohol-based fuel with high economic value, thereby improving the efficiency and economic benefits of industrial production.

[0045] In the field of fuel preparation, the utility model recovery and treatment device is used to treat the methanol waste liquid of the acetylene-aldehyde method BDO process to obtain an alcohol-based fuel that meets the requirements of the alcohol-based fuel index of GB16663. The alcohol-based fuel has the advantages of high combustion efficiency and low pollutant emissions, and is an ideal clean fuel. With the increasing global requirements for environmental protection, the market demand for alcohol-based fuels will become increasingly greater, and the utility model recovery and treatment device will have broad application prospects.

[0046] In the field of waste resource utilization, the utility model is used to recover and utilize methanol waste liquid from the acetylene-aldehyde method BDO process by using the recovery and treatment device, which can not only reduce environmental pollution but also reduce the cost of industrial production.

[0047] In general, the recycling and processing device of the utility model has broad application prospects in many fields such as chemical engineering, fuel preparation and waste resource utilization.

[0048] The present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer. Unless otherwise specified, percentages and parts are calculated by weight.

[0049] Example 1

[0050] This embodiment uses Figure 1 The recovery and treatment device of the utility model shown in the figure recovers and treats the methanol waste liquid of the acetylene-aldehyde method BDO process to prepare alcohol-based fuel.

[0051] Specifically, the composition of the methanol waste liquid of the acetylene aldehyde method BDO process obtained herein is (measured by gas chromatography):

[0052]

[0053] The specific steps are as follows:

[0054] Step 1: First, the methanol waste liquid with the above composition from the acetylene aldehyde BDO process is concentrated, and the methanol waste liquid is passed into a dehydration tower. The operating pressure in the dehydration tower is 1-10 kPaG, the operating temperature is 100-110°C, and the main components of the top vapor phase are methanol, water and trace amounts of formaldehyde, etc. At this time, the methanol concentration after concentration is ≥70wt%. The top vapor phase is condensed and pumped into a methanol decolorization reactor. The bottom liquid of the dehydration tower is a solution containing aldehydes and is sent to other devices for reuse or incineration.

[0055] Step 2: In the methanol decolorization reactor, the crude methanol is fully in contact with the catalyst, and a hydrogenation reaction occurs on the surface to hydrogenate the unsaturated organic matter contained in the methanol. This hydrogenation reaction can effectively eliminate the unsaturated bonds in the methanol and reduce the color and odor of the methanol. The reaction temperature is 150-200°C, the reaction pressure is 1-3MPaG, and the reaction time is 1-2 hours.

[0056] Step 3: After the bottom liquid phase of the methanol decolorization reactor is depressurized by a regulating valve, the catalyst powder is removed by filtering, and the hydrogen dissolved in the methanol is flash-evaporated in a vapor-liquid separation tank to obtain an alcohol-based fuel.

[0057] After the above process, the formaldehyde test of alcohol-based fuel meets the index requirements of GB16663 alcohol-based fuel (magenta does not change to blue). This treatment method can provide the economic value of methanol waste liquid in an economical and energy-saving way, reduce the cost of BDO by acetylene-aldehyde process, and has great application significance.

[0058] In summary, the use of the device of the utility model to recycle the methanol waste liquid of the acetylene-aldehyde method BDO process can simplify the process of methanol waste liquid recycling and treatment, and can convert the methanol waste liquid into alcohol-based fuel, which not only improves the economic value of the methanol waste liquid, but also reduces environmental pollution.

Claims

1. A recycling device, characterized in that: The recovery and treatment device comprises a dehydration tower connected to the methanol waste liquid outlet of the acetylene aldehyde process 1,4-butanediol production device, a conveying device connected to the top outlet of the dehydration tower, and a methanol decolorization reactor connected to the conveying device.

2. The recycling device according to claim 1, characterized in that: The conveying equipment includes a top condenser connected to the top outlet of the dehydration tower, and a distillation pump connected to the top condenser, wherein the distillation pump is used to pump a portion of the liquid cooled in the top condenser into the methanol decolorization reactor and the remaining portion into the dehydration tower.

3. The recycling device according to claim 2, characterized in that: A distillation tank is also provided between the tower top condenser and the distillation pump.

4. The recycling device according to claim 1, characterized in that: The methanol decolorization reactor is a hydrogenation reactor; The top of the methanol decolorization reactor is provided with an air inlet; A discharge port is provided at the bottom of the methanol decolorization reactor; A gas outlet is arranged on the side wall of the methanol decolorization reactor, and the gas outlet is close to the discharge port.

5. The recycling device according to claim 4, characterized in that: The recovery and processing device also includes a methanol filter connected to the discharge port of the methanol decolorization reactor.

6. The recycling device according to claim 5, characterized in that: The recovery and processing device also includes a vapor-liquid separation tank connected to the discharge port of the methanol filter.

7. The recycling device according to claim 6, characterized in that: The recovery and processing device also includes a tail gas condenser connected to the gas outlet of the vapor-liquid separation tank.

8. The recycling device according to claim 1, characterized in that: The recovery and processing device also includes a reboiler connected to the bottom outlet of the dehydration tower.

9. The recycling device according to claim 1, characterized in that: The recovery and processing device also includes a bottom pump connected to the bottom outlet of the dehydration tower.

10. The recycling device according to claim 1, characterized in that: The dehydration tower is a distillation tower; The dehydration tower adopts a fixed valve tower tray.

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