CN102617322A - Method for producing methanoic acid by adopting reactive rectification technology - Google Patents
Method for producing methanoic acid by adopting reactive rectification technology Download PDFInfo
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Abstract
The invention discloses a method for producing methanoic acid by adopting a reactive rectification technology. The method comprises the following steps of: performing homogeneous reaction on methyl formate and a part of raw material water in a hydrolysis reactor; flashing reaction products, respectively conveying a vapor phase material and a liquid phase material to the middle upper part and middle lower part of a first rectification tower, and adding the other part of raw material water from the top of the tower; extracting a material rich in methyl alcohol from a side line between a vapor phase material feeding position and a liquid phase material feeding position of the first rectification tower, and adding the material rich in methyl alcohol into a second rectification tower for deep separation; and obtaining products, namely methanoic acid product and methyl alcohol, respectively at the bottoms of the two rectification towers. According to the method, hydrolysis reaction is promoted in the first rectification tower to the maximum extent, and esterification is inhibited, so that a relatively high one-way hydrolysis conversion rate is achieved; under the condition that the water and ester feeding mole ratio is (2-4):1, the one-way hydrolysis conversion rate can be increased from 20 percent to 40-55 percent; and therefore, the methyl formate circulation amount and the energy consumption are reduced remarkably, energy can be saved by about 20-30 percent in the whole process, and remarkable economic benefits can be realized.
Description
Technical field
The present invention relates to a kind of working method of formic acid, relating in particular in a kind of carbon one Chemical Manufacture with CO and methyl alcohol is raw material carbonyl compound formic acid methyl esters, and the one-step hydrolysis of going forward side by side is produced the method for formic acid.
Background technology
Formic acid is a kind of important C1 industrial chemicals, and its working method mainly contains sodium formate method and methyl formate hydrolysis method; Sodium formate method is a working method early, has that production technique is backward, cost is high, environmental pollution is serious and is difficult to problem such as large scale continuous prod, is only applicable to small-sized Chemical Manufacture.
The methyl formate hydrolysis method is the continuous production method that generally adopts at present, is that methyl-formiate is hydrolyzed to formic acid and methyl alcohol earlier, again with the traditional method of hydrolysate rectifying separation; Because the methyl formate hydrolysis equilibrium constant lower (being about 0.2 under the temperature of reaction); Formic acid that reaction generates and methyl alcohol are easy to take place the resterification reaction and generate methyl-formiate again in the rectifying separation process; Thereby the clean percent hydrolysis of one way is lower in feasible the production, and existing production technique one way percent hydrolysis under raw water ester mol ratio 2-4:1 condition generally has only about 20%, owing to need a large amount of unhydrolysed methyl-formiates are further separated purification recycling use; Cause load bigger, energy consumption is higher.
In recent years, methyl formate hydrolysis technology has been carried out a large amount of research both at home and abroad; U.S. Pat 4299981A discloses a kind of hydrolysis reaction and has combined flash distillation round-robin method; This method at first flashes off a part of unhydrolysed methyl-formiate with the hydrolysate step-down of reactor drum and returns hydrolysis reactor and continue reaction; The remaining material entering that still contains the part methyl-formiate is presorted tower and is separated; Obtain methyl-formiate and carbinol mixture from presorting cat head; The tower still obtains aqueous formic acid, and then cat head is separated purification respectively again with bottom product; Because the part methyl-formiate is flashed out, the content of formic acid and methyl alcohol improves in the remaining product, reverse esterification can take place in presorting tower cause the one way percent hydrolysis to reduce; In order to avoid this phenomenon as far as possible, proposed to presort tower and under negative pressure, operated, make along the service temperature of tower and reduce to suppress the resterification of formic acid and methyl alcohol; This technology not only flow process is complicated, and the reduction of presorting pressure tower also can cause the overhead condensation temperature to decline to a great extent, and needs to consume a large amount of low temperature refrigerants; Chinese patent CN101481304A discloses a kind of cation exchange resin as catalyst method that the hydrolysis methyl-formiate is produced formic acid in reaction fractionating tower of utilizing; This method technical process is short; Operation can make the per pass conversion of methyl formate hydrolysis reach 70-90% under optimal conditions; But because of the work-ing life and the stability problem of catalyzer, difficulty is generalized in the maximization continuous flow procedure.
Realistic problems such as the present invention is low with existing per pass conversion in the present industrial production, operational requirement height are foundation; Per pass conversion to improve methyl formate hydrolysis is an origin with cutting down the consumption of energy, and has proposed a kind of novel method that adopts reaction rectification technique to produce formic acid.
Summary of the invention
The objective of the invention is to the deficiency to existing production technology, provide a kind of methyl formate hydrolysis to produce the method for formic acid, this method can effectively be controlled the incidence of reverse esterification, realizes higher one way hydrolysis conversion.
The objective of the invention is to realize through following technical scheme: a kind of method that adopts reaction rectification technique to produce formic acid, this method may further comprise the steps:
(1) require to confirm the flow of the fresh methyl-formiate raw material that the unit time need handle according to production task, press the flow of the total raw material water of water ester raw materials components mole ratio 2-4:1 calculating needs.
(2) fresh methyl-formiate raw material is delivered to through the methyl-formiate feedstock pump and is sent into reactor drum after the methyl-formiate feed heater is heated to 80-120 ℃; Raw water is delivered to through water transfer pump and is divided into the first rectifying tower raw water and reactor feedstocks water after the raw water well heater also is heated to 80-120 ℃, and the first rectifying tower raw water and reactor feedstocks water ratio are 0.5-2:1; Reactor feedstocks water is sent into reactor drum, and the first rectifying tower raw water is sent into first rectifying tower 3-7 piece theoretical stage place from the top down.
(3) circulation methyl-formiate material and the reactor feedstocks water hydrolytic reactions under reactor pressure 0.5-1.5MPa returned of fresh methyl-formiate raw material, subsequent technique circulation; Hydrolysate is delivered to flash tank, flash tank pressure 0.1-0.5MPa, temperature 50-100 ℃ down heating vaporization back form vapor-phase material and liquid phase material; Vapor-phase material and liquid phase material are delivered to first rectifying tower 6-10 and 14-18 piece theoretical stage place from the top down respectively; The first rectifying tower number of theoretical plate is the 20-30 piece, and working pressure is 0-0.3MPa, and side line extraction mouth is located at first rectifying tower 10-14 piece theoretical stage place from the top down; Regulate the flow of a tower reboiler heating steam, control first rectifying tower column bottom temperature 110-160 ℃, make at the bottom of the tower of first rectifying tower to not containing the pure aqueous formic acid of methyl-formiate and methyl alcohol; Aqueous formic acid is discharged at the bottom of the tower of first rectifying tower; Rising steam gets into a tower condensing surface in first rectifying tower, is that 1-4 operates by reflux ratio after the condensation; Cat head obtains unhydrolysed methyl-formiate and delivers to circulation methyl-formiate product pump, and the vapor-phase material that methyl alcohol is rich in the side line extraction is sent into second rectifying tower.
(4) vapor-phase material of the first rectifying tower side line extraction is sent into second rectifying tower 10-16 piece theoretical stage place from the top down; The second rectifying tower number of theoretical plate is the 20-30 piece, and working pressure is 0-0.3MPa; Regulate the flow of two tower reboiler heating steams, control second rectifying tower column bottom temperature 70-120 ℃, make at the bottom of the tower of second rectifying tower to not containing the pure methanol aqueous solution of methyl-formiate; Methanol aqueous solution is discharged at the bottom of the tower of second rectifying tower; Rising steam gets into two tower condensing surfaces in second rectifying tower; Be that 1-4 operates by reflux ratio after the condensation; Methyl-formiate that the first rectifying tower side line is taken out of and the methyl-formiate that resterification generates in second rectifying tower are delivered to circulation methyl-formiate product pump from the cat head of second rectifying tower; The unhydrolysed methyl-formiate that obtains with the first rectifying tower cat head mixes, and forms circulation methyl-formiate material.
(5) circulation methyl-formiate product pump methyl-formiate that first rectifying tower and the second rectifying tower cat head are sent here is delivered to circulation methyl-formiate material heater heats and after 80-120 ℃, is sent into reactor drum; With reactor feedstocks water and fresh methyl-formiate raw materials mix hydrolytic reactions under reactor pressure 0.5-1.5MPa, hydrolysate is delivered to flash tank.
Beneficial effect of the present invention is:
(1) technology of the present invention is simple, the extraction at the bottom of first rectifying tower of the formic acid of one of hydrolysate, and another product methyl alcohol is all extraction at the bottom of second rectifying tower then.
(2) material of two rectifying tower top extraction of the present invention need not carry out separating again of methyl-formiate and methyl alcohol, can direct cycle to reactor drum and participate in reaction, and contained small amount of methanol can make to be reflected in the homogeneous liquid phase and carry out in the material, can improve hydrolysis rate.
(3) the present invention suppresses the resterification reaction in the rectifying tower through side line extraction methyl alcohol, can realize higher one way hydrolysis conversion (40-55%), thereby unhydrolysed methyl-formiate internal circulating load declines to a great extent, and can reduce the energy expenditure of total system.Calculating shows, adopts the present invention to compare with current technology and can save energy about 20-30%.
(4) the present invention is easy to operate, and the proportioning raw materials of reactor drum can be grasped flexibly, is easy to carry out serialization scale operation.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Among the figure, fresh methyl-formiate raw material 1, raw water 2, circulation methyl-formiate material 3, methyl-formiate feedstock pump 4, water transfer pump 5, circulation methyl-formiate product pump 6, methyl-formiate feed heater 7, raw water well heater 8, circulation methyl-formiate material well heater 9, reactor drum 10, flash tank 11, first rectifying tower 12, a tower condensing surface 13, a tower reboiler 14, side line extraction material 15, second rectifying tower 16, two tower condensing surfaces 17, two tower reboilers 18, a bottom product 19, two bottom products 20, reactor feedstocks water 21, the first rectifying tower raw water 22, vapor-phase material 23, liquid phase material 24.
Embodiment
The method that a kind of methyl formate hydrolysis reactive distillation that the present invention proposes is produced formic acid may further comprise the steps:
1. require to confirm the flow of the fresh methyl-formiate raw material 1 that the unit time need handle according to production task, press the flow of the total raw material water 2 of water ester raw materials components mole ratio 2-4:1 calculating needs.
2. fresh methyl-formiate raw material 1 is delivered to through methyl-formiate feedstock pump 4 and is sent into reactor drum 10 after methyl-formiate feed heater 7 is heated to 80-120 ℃; Raw water 2 delivers to through water transfer pump 5 that to be divided into the first rectifying tower raw water 22 after raw water well heater 8 also is heated to 80-120 ℃ be 0.5-2:1 with reactor feedstocks water 21, the first rectifying tower raw waters 22 with reactor feedstocks water 21 ratios; Reactor feedstocks water 21 is sent into reactor drum 10, the first rectifying tower raw waters 22 and is sent into first rectifying tower 12 3-7 piece theoretical stage place from the top down.
3. circulation methyl-formiate material 3 and reactor feedstocks water 21 hydrolytic reactions under reactor pressure 0.5-1.5MPa that fresh methyl-formiate raw material 1, subsequent technique circulation are returned; Hydrolysate is delivered to flash tank 11, flash tank 11 pressure 0.1-0.5MPa, temperature 50-100 ℃ down heating vaporization back form vapor-phase material 23 and liquid phase material 24; Vapor-phase material 23 is delivered to first rectifying tower 12 6-10 and 14-18 piece theoretical stage place from the top down respectively with liquid phase material 24; First rectifying tower, 12 number of theoretical plates are the 20-30 piece, and working pressure is 0-0.3MPa, and side line extraction mouth is located at first rectifying tower 12 10-14 piece theoretical stage place from the top down; Regulate the flow of a tower reboiler 14 heating steams, control first rectifying tower 12 column bottom temperature 110-160 ℃, make at the bottom of the tower of first rectifying tower 12 to not containing the pure aqueous formic acid of methyl-formiate and methyl alcohol; Aqueous formic acid is discharged at the bottom of the tower of first rectifying tower 12; The rising steam get into a tower condensing surface 13 in first rectifying tower 12, are that 1-4 operates by reflux ratio after the condensation; Cat head obtains unhydrolysed methyl-formiate and delivers to circulation methyl-formiate product pump 6, and the vapor-phase material 15 that methyl alcohol is rich in the side line extraction is sent into second rectifying tower 16.
4. the vapor-phase material 15 of first rectifying tower, 12 side line extraction is sent into second rectifying tower 16 10-16 piece theoretical stage place from the top down; Second rectifying tower, 16 number of theoretical plates are the 20-30 piece, and working pressure is 0-0.3MPa; Regulate the flow of two tower reboilers, 18 heating steams, control second rectifying tower 16 column bottom temperature 70-120 ℃, make at the bottom of the tower of second rectifying tower 16 to not containing the pure methanol aqueous solution of methyl-formiate; Methanol aqueous solution is discharged at the bottom of the tower of second rectifying tower 16; Rising steam gets into two tower condensing surfaces 17 in second rectifying tower 16; Be that 1-4 operates by reflux ratio after the condensation; Methyl-formiate that first rectifying tower, 12 side lines are taken out of and the methyl-formiate that resterification generates in second rectifying tower 16 are delivered to circulation methyl-formiate product pump 6 from the cat head of second rectifying tower 16; The unhydrolysed methyl-formiate that obtains with first rectifying tower, 12 cats head mixes, and forms circulation methyl-formiate material 3.
5. circulation methyl-formiate product pump 6 methyl-formiate that first rectifying tower 12 and second rectifying tower, 16 cats head are sent here is delivered to and is sent into reactor drum 10 after circulation methyl-formiate material well heater 9 is heated to 80-120 ℃; Be blended in hydrolytic reactions under the reactor pressure 0.5-1.5MPa with reactor feedstocks water 21 and fresh methyl-formiate raw material 1, hydrolysate is delivered to flash tank 11.
Among the present invention; Reactor drum 10 can be for formic acid being the tubular type homogeneous reactor of autocatalysis agent; Flash tank 11 can be the common heating evaporating pot of jacketed, coil pipe or shell and tube, and first rectifying tower 12 and second rectifying tower 16 all can be tray column or packing tower commonly used.
From the material of first rectifying tower, 12 side line extraction can be vapour phase, can be liquid phase also, is preferably vapour phase.The vapour phase of side line extraction can directly get into second rectifying tower 16, also can get into second rectifying tower 16 again behind the condensation liquefaction.
Formic acid content is 55-70wt% the aqueous formic acid that obtains at the bottom of first rectifying tower, 12 towers, and all the other are water; Containing methanol content in the side line extraction material is 50-70wt%, and formic acid content is 0.5-2.5wt%, and methyl-formiate content is 15-35wt%, and all the other are water; Methanol content is 65-85wt% in the methanol aqueous solution that obtains at the bottom of second rectifying tower, 16 towers, and all the other are water.
Among the present invention, the vapor-phase material 23 that reaction product forms in flash tank 11 internal heating vaporization back and liquid phase material 24 are respectively from the middle and upper part and the middle and lower part charging of first rectifying tower 12; For the top charging, methyl alcohol, formic acid and water are assembled downwards as heavy constituent; For underfeed, methyl-formiate and methyl alcohol are upwards assembled as light constituent again; The acting in conjunction of two bursts of chargings is that the region intermediate at two opening for feeds forms a methyl alcohol enrichment region; As with the extraction in the tower in good time of the material in the methyl alcohol enrichment region, will make in the tower that methanol content descends greatly in each column plate liquid phase, help promoting hydrolysis; In addition, because first rectifying tower top adds the first additional rectifying tower raw water 22 again, with the further hydrolysis that more helps impelling methyl-formiate; But near the inrichment owing to methyl alcohol the extraction district possibly cause taking place in this place's tower reverse esterification; The applicant finds through a large amount of experiments, is rich in the vapor-phase material of methyl alcohol through the side line extraction, and percent hydrolysis can be significantly greater than the resterification rate in whole tower, and net effect is that hydrolysis reaction is more preponderated in the tower.
For the material that prevents extraction contains more formic acid, can make side line extraction material is vapour phase; But nonetheless still can contain a spot of formic acid in the material, cause formic acid can not be all extraction at the bottom of first rectifying tower; In order to simplify follow-up separation process; The a small amount of formic acid that in second rectifying tower 16, will bring into and methyl alcohol generation esterification regeneration methyl-formiate; The methyl-formiate of self bringing into together with the side line material steams Returning reactor from the cat head of second rectifying tower 16, can obtain not contain the methanol aqueous solution of formic acid at the bottom of the tower of second rectifying tower 16.
According to said technology, adopt one way hydrolysis conversion of the present invention can reach 40-55%, be superior to current traditional technology one way hydrolysis conversion and be not higher than 20% level.
Through specific embodiment the present invention is done further description below, but should the present invention be interpreted as and be only applicable to following case.
Embodiment 1
Shown in accompanying drawing 1, flow is that water charging feed water heater 8 after water transfer pump 5 is pressurized to 0.8MPa (gauge pressure) of 3180kg/h is heated to 100 ℃, is split into the first rectifying tower raw water 22 (1590kg/h) and reactor feedstocks water 21 (1590kg/h).Flow is that (containing methyl-formiate is 98.5% for the fresh methyl-formiate raw material of 4140kg/h; Formic acid 0.5%; Water 1.0%) after methyl-formiate feedstock pump 4 is pressurized to 0.8MPa (gauge pressure), send into methyl-formiate feed heater 7 and be heated to 100 ℃ of entering reactor drums 10; The material that reactor drum is discharged gets into flash tank 11; Flash tank 11 is in pressure 0.12MPa (gauge pressure), temperature 60-65 ℃ vaporization down, and vapor-phase material 23 gets into first rectifying tower the 6th and the 14th theoretical stage place (the total theoretical stage of this tower is 20) from the top down respectively with liquid phase material 24, and the first rectifying tower raw water 22 gets into this tower the 3rd theoretical stage place from the top down.
Get into the 10th theoretical stage (the total theoretical stage of this tower is 20) of second rectifying tower 16 at the 10th block of theoretical stage place vapour phase extraction material 15 of first rectifying tower 12.The circulation methyl-formiate material 3 of two cat head extraction is pressurized to 0.8MPa (gauge pressure) through circulation methyl-formiate product pump 6 and delivers to and send into reactor drum 10 after circulation methyl-formiate material well heater 9 is heated to 100 ℃.
First rectifying tower, 12 tower top pressures are 0.11MPa (gauge pressure), and temperature is 54.9 ℃, and reflux ratio is 2.5; Second rectifying tower, 16 tower top pressures are 0.1MPa (gauge pressure), and temperature is 53.3 ℃, and reflux ratio is 3.5; Obtaining circulation methyl-formiate material 3 flows behind the stable operation is 5987kg/h; Obtaining mass flow at the bottom of first rectifying tower is 4687kg/h (formic acid content 67.1wt%); Temperature is 133-138 ℃; Obtaining mass flow at the bottom of second rectifying tower is 2633kg/h (methanol content 82.6wt%), and temperature is 86-91 ℃.
According to the logistics result, the total mol ratio of actual water ester charging is 2.6:1, and the first rectifying tower raw water 22 is 1:1 with reactor feedstocks water 21 partition ratios, and can get the total hydrolysis conversion of one way is 43.1%.
Embodiment 2
Shown in accompanying drawing 1, flow is that water charging feed water heater 8 after water transfer pump 5 is pressurized to 0.6MPa (gauge pressure) of 3670kg/h is heated to 80 ℃, is split into the first rectifying tower raw water 22 (1835kg/h) and reactor feedstocks water 21 (1835kg/h).Flow is that (containing methyl-formiate is 98.5% for the fresh methyl-formiate raw material of 4140kg/h; Formic acid 0.5%; Water 1.0%) after methyl-formiate feedstock pump 4 is pressurized to 0.6MPa (gauge pressure), send into methyl-formiate feed heater 7 and be heated to 80 ℃ of entering reactor drums 10; The material that reactor drum is discharged gets into flash tank 11; Flash tank 11 is in pressure 0.12MPa (gauge pressure), temperature 60-65 ℃ vaporization down, and vapor-phase material 23 gets into first rectifying tower the 6th and the 14th theoretical stage place (the total theoretical stage of this tower is 20) from the top down respectively with liquid phase material 24, and the first rectifying tower raw water 22 gets into this tower the 3rd theoretical stage place from the top down.
Get into the 13rd theoretical stage (the total theoretical stage of this tower is 25) of second rectifying tower 16 at the 10th block of theoretical stage place vapour phase extraction material 15 of first rectifying tower 12.The circulation methyl-formiate material 3 of two cat head extraction is pressurized to 0.6MPa (gauge pressure) through circulation methyl-formiate product pump 6 and delivers to and send into reactor drum 10 after circulation methyl-formiate material well heater 9 is heated to 80 ℃.
First rectifying tower, 12 tower top pressures are 0.11MPa (gauge pressure), and temperature is 55.4 ℃, and reflux ratio is 2.5; Second rectifying tower, 16 tower top pressures are 0.1MPa (gauge pressure), and temperature is 53.3 ℃, and reflux ratio is 3.5; Obtaining circulation methyl-formiate material 3 flows behind the stable operation is 5192kg/h; Obtaining mass flow at the bottom of first rectifying tower is 5040kg/h (formic acid content 62.4wt%); Temperature is 131-136 ℃; Obtaining mass flow at the bottom of second rectifying tower is 2770kg/h (methanol content 78.5wt%), and temperature is 89-94 ℃.
According to the logistics result, the total mol ratio of actual water ester charging is 3.0:1, and the first rectifying tower raw water 22 is 1:1 with reactor feedstocks water 21 partition ratios, and can get the total hydrolysis conversion of one way is 46.6%.
Embodiment 3
Shown in accompanying drawing 1, flow is that water charging feed water heater 8 after water transfer pump 5 is pressurized to 1.2MPa (gauge pressure) of 3670kg/h is heated to 120 ℃, is split into the first rectifying tower raw water 22 (1835kg/h) and reactor feedstocks water 21 (1835kg/h).Flow is that (containing methyl-formiate is 98.5% for the fresh methyl-formiate raw material of 4140kg/h; Formic acid 0.5%; Water 1.0%) after methyl-formiate feedstock pump 4 is pressurized to 1.2MPa (gauge pressure), send into methyl-formiate feed heater 7 and be heated to 120 ℃ of entering reactor drums 10; The material that reactor drum is discharged gets into flash tank 11; Flash tank 11 is in pressure 0.22MPa (gauge pressure), temperature 73-78 ℃ vaporization down, and vapor-phase material 23 gets into first rectifying tower the 10th and the 18th theoretical stage place (the total theoretical stage of this tower is 30) from the top down respectively with liquid phase material 24, and the first rectifying tower raw water 22 gets into this tower the 6th theoretical stage place from the top down.
Get into the 15th theoretical stage (the total theoretical stage of this tower is 30) of second rectifying tower 16 at the 14th block of theoretical stage place vapour phase extraction material 15 of first rectifying tower 12.The circulation methyl-formiate material 3 of two cat head extraction is pressurized to 1.2MPa (gauge pressure) through circulation methyl-formiate product pump 6 and delivers to and send into reactor drum 10 after circulation methyl-formiate material well heater 9 is heated to 120 ℃.
First rectifying tower, 12 tower top pressures are 0.21MPa (gauge pressure), and temperature is 68.8 ℃, and reflux ratio is 2; Second rectifying tower, 16 tower top pressures are 0.2MPa (gauge pressure), and temperature is 66.5 ℃, and reflux ratio is 2; Obtaining circulation methyl-formiate material 3 flows behind the stable operation is 4735kg/h; Obtaining mass flow at the bottom of first rectifying tower is 5043kg/h (formic acid content 62.4wt%); Temperature is 142-147 ℃; Obtaining mass flow at the bottom of second rectifying tower is 2767kg/h (methanol content 78.6wt%), and temperature is 105-110 ℃.
According to the logistics result, the total mol ratio of actual water ester charging is 3.0:1, and the first rectifying tower raw water 22 is 1:1 with reactor feedstocks water 21 partition ratios, and can get the total hydrolysis conversion of one way is 48.9%.
Embodiment 4
Shown in accompanying drawing 1, flow is that water charging feed water heater 8 after water transfer pump 5 is pressurized to 0.8MPa (gauge pressure) of 4282kg/h is heated to 100 ℃, is split into the first rectifying tower raw water 22 (1427kg/h) and reactor feedstocks water 21 (2855kg/h).Flow is that (containing methyl-formiate is 98.5% for the fresh methyl-formiate raw material of 4140kg/h; Formic acid 0.5%; Water 1.0%) after methyl-formiate feedstock pump 4 is pressurized to 0.8MPa (gauge pressure), send into methyl-formiate feed heater 7 and be heated to 100 ℃ of entering reactor drums 10; The material that reactor drum is discharged gets into flash tank 11; Flash tank 11 is in pressure 0.12MPa (gauge pressure), temperature 63-68 ℃ vaporization down, and vapor-phase material 23 gets into first rectifying tower the 8th and the 16th theoretical stage place (the total theoretical stage of this tower is 25) from the top down respectively with liquid phase material 24, and the first rectifying tower raw water 22 gets into this tower the 4th theoretical stage place from the top down.
Get into the 13rd theoretical stage (the total theoretical stage of this tower is 25) of second rectifying tower 16 at the 12nd block of theoretical stage place vapour phase extraction material 15 of first rectifying tower 12.The circulation methyl-formiate material 3 of two cat head extraction is pressurized to 0.8MPa (gauge pressure) through circulation methyl-formiate product pump 6 and delivers to and send into reactor drum 10 after circulation methyl-formiate material well heater 9 is heated to 100 ℃.
First rectifying tower, 12 tower top pressures are 0.11MPa (gauge pressure), and temperature is 55.8 ℃, and reflux ratio is 2.5; Second rectifying tower, 16 tower top pressures are 0.1MPa (gauge pressure), and temperature is 53.5 ℃, and reflux ratio is 3; Obtaining circulation methyl-formiate material 3 flows behind the stable operation is 5353kg/h; Obtaining mass flow at the bottom of first rectifying tower is 5319kg/h (formic acid content 59.2wt%); Temperature is 130-135 ℃; Obtaining mass flow at the bottom of second rectifying tower is 3103kg/h (methanol content 70.1wt%), and temperature is 92-97 ℃.
According to the logistics result, the total mol ratio of actual water ester charging is 3.5:1, and the first rectifying tower raw water 22 is 0.5:1 with reactor feedstocks water 21 partition ratios, and can get the total hydrolysis conversion of one way is 46.4%.
Embodiment 5
Shown in accompanying drawing 1, flow is that water charging feed water heater 8 after water transfer pump 5 is pressurized to 0.8MPa (gauge pressure) of 4282kg/h is heated to 100 ℃, is split into the first rectifying tower raw water 22 (2855kg/h) and reactor feedstocks water 21 (1427kg/h).Flow is that (containing methyl-formiate is 98.5% for the fresh methyl-formiate raw material of 4140kg/h; Formic acid 0.5%; Water 1.0%) after methyl-formiate feedstock pump 4 is pressurized to 0.8MPa (gauge pressure), send into methyl-formiate feed heater 7 and be heated to 100 ℃ of entering reactor drums 10; The material that reactor drum is discharged gets into flash tank 11; Flash tank 11 is in pressure 0.22MPa (gauge pressure), temperature 75-80 ℃ vaporization down, and vapor-phase material 23 gets into first rectifying tower the 8th and the 16th theoretical stage place (the total theoretical stage of this tower is 25) from the top down respectively with liquid phase material 24, and the first rectifying tower raw water 22 gets into this tower the 4th theoretical stage place from the top down.
Get into the 13rd theoretical stage (the total theoretical stage of this tower is 25) of second rectifying tower 16 at the 12nd block of theoretical stage place vapour phase extraction material 15 of first rectifying tower 12.The circulation methyl-formiate material 3 of two cat head extraction is pressurized to 0.8MPa (gauge pressure) through circulation methyl-formiate product pump 6 and delivers to and send into reactor drum 10 after circulation methyl-formiate material well heater 9 is heated to 100 ℃.
First rectifying tower, 12 tower top pressures are 0.21MPa (gauge pressure), and temperature is 70.5 ℃, and reflux ratio is 3.5; Second rectifying tower, 16 tower top pressures are 0.2MPa (gauge pressure), and temperature is 67.7 ℃, and reflux ratio is 3.5; Obtaining circulation methyl-formiate material 3 flows behind the stable operation is 4105kg/h; Obtaining mass flow at the bottom of first rectifying tower is 5288kg/h (formic acid content 59.5wt%); Temperature is 141-146 ℃; Obtaining mass flow at the bottom of second rectifying tower is 3134kg/h (methanol content 69.4wt%), and temperature is 108-113 ℃.
According to the logistics result, the total mol ratio of actual water ester charging is 3.5:1, and the first rectifying tower raw water 22 is 2:1 with reactor feedstocks water 21 partition ratios, and can get the total hydrolysis conversion of one way is 53.6%.
Claims (3)
1. one kind is that raw material adopts reaction rectification technique to produce the method for formic acid with the methyl-formiate, it is characterized in that this method may further comprise the steps:
(1) require to confirm the flow of the fresh methyl-formiate raw material that the unit time need handle according to production task, press the flow of the total raw material water of water ester raw materials components mole ratio 2-4:1 calculating needs;
(2) fresh methyl-formiate raw material is delivered to through the methyl-formiate feedstock pump and is sent into reactor drum after the methyl-formiate feed heater is heated to 80-120 ℃; Raw water is delivered to through water transfer pump and is divided into the first rectifying tower raw water and reactor feedstocks water after the raw water well heater also is heated to 80-120 ℃, and the first rectifying tower raw water and reactor feedstocks water ratio are 0.5-2:1; Reactor feedstocks water is sent into reactor drum, and the first rectifying tower raw water is sent into first rectifying tower 3-7 piece theoretical stage place from the top down;
(3) circulation methyl-formiate material and the reactor feedstocks water hydrolytic reactions under reactor pressure 0.5-1.5MPa returned of fresh methyl-formiate raw material, subsequent technique circulation; Hydrolysate is delivered to flash tank, flash tank pressure 0.1-0.5MPa, temperature 50-100 ℃ down heating vaporization back form vapor-phase material and liquid phase material; Vapor-phase material and liquid phase material are delivered to first rectifying tower 6-10 and 14-18 piece theoretical stage place from the top down respectively; The first rectifying tower number of theoretical plate is the 20-30 piece, and working pressure is 0-0.3MPa, and side line extraction mouth is located at first rectifying tower 10-14 piece theoretical stage place from the top down; Regulate the flow of a tower reboiler heating steam, control first rectifying tower column bottom temperature 110-160 ℃, make at the bottom of the tower of first rectifying tower to not containing the pure aqueous formic acid of methyl-formiate and methyl alcohol; Aqueous formic acid is discharged at the bottom of the tower of first rectifying tower; Rising steam gets into a tower condensing surface in first rectifying tower, is that 1-4 operates by reflux ratio after the condensation; Cat head obtains unhydrolysed methyl-formiate and delivers to circulation methyl-formiate product pump, and the vapor-phase material that methyl alcohol is rich in the side line extraction is sent into second rectifying tower;
(4) vapor-phase material of the first rectifying tower side line extraction is sent into second rectifying tower 10-16 piece theoretical stage place from the top down; The second rectifying tower number of theoretical plate is the 20-30 piece, and working pressure is 0-0.3MPa; Regulate the flow of two tower reboiler heating steams, control second rectifying tower column bottom temperature 70-120 ℃, make at the bottom of the tower of second rectifying tower to not containing the pure methanol aqueous solution of methyl-formiate; Methanol aqueous solution is discharged at the bottom of the tower of second rectifying tower; Rising steam gets into two tower condensing surfaces in second rectifying tower; Be that 1-4 operates by reflux ratio after the condensation; Methyl-formiate that the first rectifying tower side line is taken out of and the methyl-formiate that resterification generates in second rectifying tower are delivered to circulation methyl-formiate product pump from the cat head of second rectifying tower; The unhydrolysed methyl-formiate that obtains with the first rectifying tower cat head mixes, and forms circulation methyl-formiate material;
(5) circulation methyl-formiate product pump circulation methyl-formiate material that first rectifying tower and the second rectifying tower cat head are sent here is delivered to circulation methyl-formiate material heater heats and after 80-120 ℃, is sent into reactor drum; With reactor feedstocks water and fresh methyl-formiate raw materials mix hydrolytic reactions under reactor pressure 0.5-1.5MPa, hydrolysate is delivered to flash tank.
2. the method for producing formic acid according to the said employing reaction rectification technique of claim 1; It is characterized in that; Reactor drum can be for formic acid being the tubular type homogeneous reactor of autocatalysis agent; Flash tank can be the common heating evaporating pot of jacketed, coil pipe or shell and tube, and first rectifying tower and second rectifying tower all can be tray column or packing tower commonly used.
3. producing the method for formic acid according to the said employing reaction rectification technique of claim 1, it is characterized in that, can be vapour phase from the material of the first rectifying tower side line extraction, can be liquid phase also, is preferably vapour phase; The vapour phase of side line extraction can directly get into second rectifying tower, also can get into second rectifying tower again behind the condensation liquefaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3428321C2 (en) * | 1984-08-01 | 1987-06-25 | Huels Ag, 4370 Marl, De | |
| CN1407960A (en) * | 1999-10-13 | 2003-04-02 | 苏舍化学技术有限公司 | Process and devices for hydrolytically obtaining carboxylic acid and alcohol from corresponding carboxylate |
| CN101125795A (en) * | 2007-09-30 | 2008-02-20 | 四川天一科技股份有限公司 | Method for preparing formic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3428321C2 (en) * | 1984-08-01 | 1987-06-25 | Huels Ag, 4370 Marl, De | |
| CN1407960A (en) * | 1999-10-13 | 2003-04-02 | 苏舍化学技术有限公司 | Process and devices for hydrolytically obtaining carboxylic acid and alcohol from corresponding carboxylate |
| CN101125795A (en) * | 2007-09-30 | 2008-02-20 | 四川天一科技股份有限公司 | Method for preparing formic acid |
Non-Patent Citations (1)
| Title |
|---|
| 陈云华等: "甲酸甲酯水解工艺的研究", 《云南化工》, vol. 27, no. 2, 30 April 2000 (2000-04-30), pages 3 - 5 * |
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