CN102126943B - Recycling and separating process of heavy component residual liquid in carbonylation production process of acetic acid - Google Patents
Recycling and separating process of heavy component residual liquid in carbonylation production process of acetic acid Download PDFInfo
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- CN102126943B CN102126943B CN201010550011A CN201010550011A CN102126943B CN 102126943 B CN102126943 B CN 102126943B CN 201010550011 A CN201010550011 A CN 201010550011A CN 201010550011 A CN201010550011 A CN 201010550011A CN 102126943 B CN102126943 B CN 102126943B
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Abstract
The invention discloses a recycling and separating process of heavy component residual liquid in the carbonylation production process of acetic acid, belonging to the separation technical field of the organic chemical engineering. The process comprises the following steps: firstly, the residual liquid is sent to a wiped film evaporator to perform reduced pressure operation and remove high polymer heavy component; and secondly, light component enters a batch distillation device to obtain the products such as acetic acid, acetoxyacetic acid and ethylene glycol diacetate through separation and purification. The invention adopts the recycling and separating process of the acetic acid heavy component residual liquid; the flow is simple, the process is easy to operate; after the high polymer heavy component is removed, the residual liquid meets the requirements of environmental protection treatment; and the products with high added value can be effectively recycled, the recovery rate is more than 90% and the process is an efficient and environmentally friendly recycling and separating process.
Description
Technical field
The invention belongs to organic chemical industry's separation technology field, relate to the recovery method of waste liquid in the Chemical Manufacture, particularly carbonylation is produced the heavy component raffinate that discharges in the acetic acid process and is reclaimed separation processes.
Background technology
Acetic acid is a kind of important basic Organic Chemicals, also is to develop a kind of faster important Organic Chemicals in recent years in the world, is mainly used in products such as producing Vinyl Acetate Monomer, cellulose acetate, aceticanhydride and metal acetate salt.By the year ends 2009, just there is more than 90 house in China acetic acid production enterprise, and throughput reaches 1,200,000 t/a, and wherein the carbonylation technology of producing acetic acid is the main flow technology of current acetic acid production with advantages such as reaction conditions are gentle, yield is high and production cost is low.According to statistics, adopt the acetic acid of this explained hereafter to account for more than 65% of global gross production at present.
Produce in the process of acetic acid in carbonylation of methanol, reaction product is through the refining acetic acid that can by-product be rich on a small quantity about 30%, about 20% glycol diacetate, about 25% acetoxy acid and the heavy component raffinate of high boiling point polymkeric substance of separating when obtaining high purity acetic acid.Obviously, the acetic acid amount that is rich in this waste liquid is higher, and glycol diacetate that contains simultaneously and acetoxy acid all are organic chemical industry's midbodys of high added value, and marketable value is very high.Can know through analyzing; For the acetic acid production enterprise that produces 100000 tons per year; Produce the acetic acid heavy component waste liquid of nearly kiloton every year on average; Each manufacturing enterprise does not all have practicable recovery and treatment method both at home and abroad at present, so that all this waste liquid is directly discharged or burns, and has not only caused the waste of resource but also environment has been caused serious pollution.
Along with the enhancing of current environmental consciousness and the sense of urgency of energy dilemma; Both at home and abroad each acetic acid production enterprise and numerous relevant high scientific research institutions all drop into the research that a large amount of material resources, manpower are carried out the high efficiente callback of acetic acid heavy component waste liquid; Therefore if can develop the recovery separating technology of this acetic acid heavy component waste liquid of a kind of high efficiente callback, will produce bigger social benefit and economic benefit.
Summary of the invention
The purpose of this invention is to provide the heavy component raffinate that discharges in a kind of carbonylation production acetic acid process and reclaim separation processes; But adopt acetic acid, glycol diacetate and the acetoxy acid product of this technology efficient recovery acetic acid heavy constituent raffinate, will reduce the acetic acid content of the heavy component raffinate of discharging simultaneously.
Technical process of the present invention is divided into luwa evaporator and removes heavy component step and two parts of batch fractionating purification step; Be that feed liquid gets into from wiped film vaporization apparatus top; Under reduced pressure; Discharge the superpolymer heavy component from the bottom through the rotating speed of adjusting scraper plate and the temperature of bottom material outlet, the light constituent that the top obtains gets into the batch fractionating unit after condensation; Under reduced pressure, obtain acetic acid, glycol diacetate and acetoxy acid product respectively through the varying reflux ratio operation.
The invention provides a kind of carbonylation and produce the recovery separating technology of heavy component raffinate in the acetic acid process, this technology comprises luwa evaporator and removes heavy component step and two parts of batch fractionating purification step, and concrete process step is following:
1) feed liquid gets into from wiped film vaporization apparatus top; At pressure is under 3.0～4.0KPa; Regulate the scraper plate rotating speed being 30.0～40.0 rev/mins is 145.0～150.0 ℃ with bottom material temperature out; Discharge the superpolymer heavy constituent to this battery limit (BL) from the bottom, the light constituent that discharge at the top gets into the batch fractionating unit after condensation;
2) the unitary pressure-controlling of batch fractionating is under the condition of 5.0～6.0KPa, treat that total reflux operation is stable after, carry out the varying reflux ratio operation:
● when reflux ratio is that 1: 1～1.5: 1, tower still temperature are under 100.0～115.0 ℃ the condition, from cat head extraction light constituent;
● in reflux ratio is that 4: 1～5: 1, tower still temperature are under 130.0～135.0 ℃ the condition, from cat head extraction acetate products;
● in reflux ratio is that 6: 1～8: 1, tower still temperature are under 150.0～155.0 ℃ the condition, from cat head extraction glycol diacetate product;
● in reflux ratio is that 8: 1～10: 1, tower still temperature are under 160.0～165.0 ℃ the condition, from cat head extraction acetoxy acid product.
● bottom product is disposed to outside the battery limit (BL).
Adopt acetic acid content in the superpolymer heavy component that technology of the present invention removes through luwa evaporator less than 500ppm; Through the batch fractionating unit obtain product purity greater than 99.0% acetic acid, purity greater than 99.0% glycol diacetate and purity greater than 99.0% acetoxy acid.
The invention has the advantages that described acetic acid heavy component raffinate reclaims separating technology; Flow process is simple, easy handling, and the superpolymer heavy component raffinate after not only removing reaches the environmental protection treatment requirement; And can reclaim high value added product acetic acid, glycol diacetate and acetoxy acid effectively; Increased resource utilization, the recovery is greater than 90%, is a kind of recovery separating technology of efficient and environmental protection.
Description of drawings
The separation process scheme figure of Fig. 1 carbonylation acetic acid of the present invention heavy component waste liquid.
The 1-raw material; The 2-luwa evaporator; The 3-surge tank, the 4-heavy constituent; The 5-condensing surface; The 6-vacuum system; 7-light constituent tundish; 8-batch fractionating unit; 9-light constituent product; The 10-acetate products; 11-glycol diacetate product; 12-acetoxy acid product; The 13-bottom product.
Embodiment
Below in conjunction with embodiment, further specify the present invention, but the present invention is not limited to embodiment.
Embodiment 1
Process flow sheet as shown in Figure 1; With the 3.8ml/min flow velocity acetic acid heavy component waste liquid is got in the luwa evaporator 2 from raw material 1, open vacuum system 6, the pressure of control luwa evaporator 2 systems is at 3.0KPa; Scraper plate speed adjustment to 30 rev/min; The bottom liquid temperature out is 145 ℃, and superpolymer heavy component 4 is discharged in surge tank 3 then outside the tower bottoms 13 eliminating battery limit (BL)s in the bottom, and acetic acid content is less than 200ppm; The top light constituent gets in the light constituent tundish 7 after condensing surface 5 condensations simultaneously, gets into then to carry out the reflux ratio operation in the batch fractionating unit 8, and system pressure control 5.0KPa treats the stable back of total reflux after about 1 hour, and concrete operations are following:
1) be that 1.5: 1, tower still temperature are under 110.0 ℃ the condition, from cat head extraction light constituent product 9 in reflux ratio;
2) be that 5: 1, tower still temperature are that from cat head extraction acetate products 10, purity is 99.2% under 130.0 ℃ the condition in reflux ratio;
3) be that 8: 1, tower still temperature are that from cat head extraction glycol diacetate product 11, purity is 99.3% under 150.0 ℃ the condition in reflux ratio;
4) be that 10: 1, tower still temperature are that from cat head extraction acetoxy acid product 12, purity is 99.0% under 160.0 ℃ the condition in reflux ratio;
5) bottom product 13 is disposed to outside the battery limit (BL).
Process flow sheet as shown in Figure 1; With the 4.5ml/min flow velocity acetic acid heavy component waste liquid is got in the luwa evaporator 2 from raw material 1, open vacuum system 6, the pressure of control luwa evaporator 2 systems is at 4.0KPa; Scraper plate speed adjustment to 40 rev/min; The bottom liquid temperature out is 150 ℃, and superpolymer heavy component 4 is got rid of in surge tank 3 then outside the bottom product 13 discharge battery limit (BL)s in the bottom, and acetic acid content is less than 420ppm; The top light constituent gets in the light constituent tundish 7 after condensing surface 5 condensations simultaneously, gets into then to carry out the reflux ratio operation in the batch fractionating unit 8, and system pressure control 6.0KPa treats the stable back of total reflux after about 1.5 hours, and concrete operations are following:
1) be that 1.2: 1, tower still temperature are under 110.0 ℃ the condition, from cat head extraction light constituent product 9 in reflux ratio;
2) be that 4.5: 1, tower still temperature are that from cat head extraction acetate products 10, purity is 99.5% under 132.0 ℃ the condition in reflux ratio;
3) be that 7: 1, tower still temperature are that from cat head extraction glycol diacetate product 11, purity is 99.1% under 152.0 ℃ the condition in reflux ratio;
4) be that 9: 1, tower still temperature are that from cat head extraction acetoxy acid product 12, purity is 99.2% under 163.0 ℃ the condition in reflux ratio;
5) bottom product 13 is disposed to outside the battery limit (BL).
Process flow sheet as shown in Figure 1; With 4m l/min flow velocity acetic acid heavy component waste liquid is got in the luwa evaporator 2 from raw material 1, open vacuum system 6, the pressure in the control luwa evaporator 2 is at 5.3KPa; Scraper plate speed adjustment to 35 rev/min; The bottom liquid temperature out is 146 ℃, and superpolymer heavy component 4 is got rid of in surge tank 3 then outside the bottom product 13 discharge battery limit (BL)s in the bottom, and acetic acid content is less than 200ppm; Simultaneously the top light constituent gets in the light constituent tundish 7 after condensing surface 5 condensations, get into then to carry out the reflux ratio operation in the batch fractionating unit 8, system pressure control 5.1KPa, treat total reflux stable after after about 1.2 hours concrete operations following:
1) be that 1: 1, tower still temperature are under 115.0 ℃ the condition, from cat head extraction light constituent product 9 in reflux ratio;
2) be that 4: 1, tower still temperature are that from cat head extraction acetate products 10, purity is 99.4% under 135.0 ℃ the condition in reflux ratio;
3) be that 6: 1, tower still temperature are that from cat head extraction glycol diacetate product 11, purity is 99.21% under 155.0 ℃ the condition in reflux ratio;
4) be that 8: 1, tower still temperature are that from cat head extraction acetoxy acid product 12, purity is 99.2% under 165.0 ℃ the condition in reflux ratio;
5) bottom product 13 is disposed to outside the battery limit (BL).
Claims (3)
1. carbonylation is produced the recovery separating technology of heavy component raffinate in the acetic acid process, it is characterized in that this technology comprises luwa evaporator and removes heavy component step and two parts of batch fractionating purification step, and concrete process step is following:
1) feed liquid gets into from wiped film vaporization apparatus top; At pressure is under 3.0～4.0KPa; Regulate the scraper plate rotating speed being 30.0～40.0 rev/mins is 145.0～150.0 ℃ with bottom material temperature out; Discharge the superpolymer heavy constituent to this battery limit (BL) from the bottom, the light constituent that discharge at the top gets into the batch fractionating unit after condensation;
2) the unitary pressure-controlling of batch fractionating is under the condition of 5.0～6.0KPa, treat that total reflux operation is stable after, carry out the varying reflux ratio operation:
● when reflux ratio is that 1: 1～1.5: 1, tower still temperature are under 100.0～115.0 ℃ the condition, from cat head extraction light constituent;
● in reflux ratio is that 4: 1～5: 1, tower still temperature are under 130.0～135.0 ℃ the condition, from cat head extraction acetate products;
● in reflux ratio is that 6: 1～8: 1, tower still temperature are under 150.0～155.0 ℃ the condition, from cat head extraction glycol diacetate product;
● in reflux ratio is that 8: 1～10: 1, tower still temperature are under 160.0～165.0 ℃ the condition, from cat head extraction acetoxy acid product.
2. carbonylation as claimed in claim 1 is produced the recovery separating technology of heavy component raffinate in the acetic acid process, and acetic acid content is less than 500ppm in the superpolymer heavy component that it is characterized in that removing through luwa evaporator.
3. carbonylation as claimed in claim 1 is produced the recovery separating technology of heavy component raffinate in the acetic acid process, it is characterized in that through the batch fractionating unit can obtain product purity greater than 99.0% acetic acid, purity greater than 99.0% glycol diacetate and purity greater than 99.0% acetoxy acid.
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| CN105237399B (en) * | 2015-10-21 | 2017-04-05 | 南京长江江宇石化有限公司 | The reactive distillation process of heavy constituent residual liquid in a kind of carbonylation production process of acetic acid |
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| CN101544557A (en) * | 2009-05-05 | 2009-09-30 | 天津大学 | Coupling rectification system and application thereof in purifying EPA, DPA, and DHA in seal oil |
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Effective date of registration: 20160120 Address after: 210047 No. 157, general road, Nanjing chemical industry park, Jiangsu, China Patentee after: NANJING CHANGJIANG JIANGYU PETROCHEMICAL Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 Yangtze River Industrial Development Zone geguan road 385 No. -8 Patentee before: NANJING YANGCHI INDUSTRY GAS Co.,Ltd. |
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Address after: 210047 157 puqiao Road, Changlu street, Jiangbei new district, Nanjing City, Jiangsu Province Patentee after: Nanjing Changjiang Jiangyu Environmental Protection Technology Co.,Ltd. Address before: No.157, puqiao Road, Nanjing Chemical Industrial Park, Jiangsu 210047 Patentee before: NANJING CHANGJIANG JIANGYU PETROCHEMICAL Co.,Ltd. |
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Address after: 210047 157 puqiao Road, Changlu street, Jiangbei new district, Nanjing City, Jiangsu Province Patentee after: Nanjing Changjiang Jiangyu Environmental Protection Technology Co.,Ltd. Address before: 210047 157 puqiao Road, Changlu street, Jiangbei new district, Nanjing City, Jiangsu Province Patentee before: Nanjing Changjiang Jiangyu Environmental Protection Technology Co.,Ltd. |
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