CN102617322B - 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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- CN102617322B CN102617322B CN201210062996.XA CN201210062996A CN102617322B CN 102617322 B CN102617322 B CN 102617322B CN 201210062996 A CN201210062996 A CN 201210062996A CN 102617322 B CN102617322 B CN 102617322B
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- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000005516 engineering process Methods 0.000 title abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 125
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000463 material Substances 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 22
- 239000012808 vapor phase Substances 0.000 claims abstract description 22
- 239000007791 liquid phase Substances 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims description 57
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 46
- 238000000605 extraction Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000000413 hydrolysate Substances 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 238000009834 vaporization Methods 0.000 claims description 9
- 230000008016 vaporization Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 6
- 238000005844 autocatalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 29
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract description 20
- 230000032050 esterification Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000007600 charging Methods 0.000 description 8
- 238000005192 partition Methods 0.000 description 5
- 239000004280 Sodium formate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carbonyl compound formic acid methyl esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 production method of formic acid, relate in particular to that in a kind of carbon one Chemical Manufacture, to take CO and methyl alcohol be raw material carbonyl compound formic acid methyl esters, the method that the one-step hydrolysis of going forward side by side is produced formic acid.
Background technology
Formic acid is a kind of important C1 industrial chemicals, and its production method mainly contains sodium formate method and methyl formate hydrolysis method; Sodium formate method is production method early, has that production technique is backward, cost is high, environmental pollution is serious and be difficult to the problems such as large scale continuous prod, is only applicable to small chemical production.
Methyl formate hydrolysis method is the continuous production method generally adopting at present, is that methyl-formiate is first hydrolyzed to formic acid and methyl alcohol, then by the traditional method of hydrolysate rectifying separation; Due to the methyl formate hydrolysis equilibrium constant lower (being 0.2 left and right under temperature of reaction), the formic acid that reaction generates and methyl alcohol are easy to occur resterification reaction and generate again methyl-formiate in rectifying separation process, thereby in making to produce, the clean percent hydrolysis of one way is lower, existing production technique one way percent hydrolysis under raw water ester mol ratio 2-4:1 condition generally only has 20% left and right, because need are used the further separating-purifying recirculation of a large amount of unhydrolysed methyl-formiates, cause load larger, energy consumption is higher.
In recent years, methyl formate hydrolysis technique has been carried out to a large amount of research both at home and abroad; US Patent No. 4299981A discloses a kind of hydrolysis reaction in conjunction with the method for flash distillation circulation; First the method flashes off the hydrolysate step-down of reactor a part of unhydrolysed methyl-formiate and returns to hydrolysis reactor continuation reaction, the remaining material that still contains part methyl-formiate enters a pre-minute tower and carries out separation, from pre-minute tower top, obtain methyl-formiate and carbinol mixture, tower reactor obtains aqueous formic acid, and then tower top and bottom product are carried out respectively to separating-purifying again; Because part methyl-formiate is flashed out, in remaining product, the content of formic acid and methyl alcohol improves, and reverse esterification can occur in pre-minute tower and cause one way percent hydrolysis to reduce; In order to avoid as far as possible this phenomenon, proposed to divide in advance tower to operate under negative pressure, make to reduce to suppress along the service temperature of tower the resterification of formic acid and methyl alcohol; This technique not only flow process is complicated, divides in advance the reduction of pressure tower also can cause overhead condensation temperature to decline to a great extent, and need to consume a large amount of low temperature refrigerants; Chinese patent CN101481304A discloses a kind of cation exchange resin as catalyst that utilizes and in reactive distillation column, has been hydrolyzed the method that methyl-formiate is produced formic acid, the method technical process is short, under optimal conditions, operation can make the per pass conversion of methyl formate hydrolysis reach 70-90%, but because of work-ing life and the stability problem of catalyzer, more difficult being generalized in maximization continuous flow procedure.
It is foundation that the realistic problems such as existing per pass conversion is low in present industrial production, operational requirement is high are take in the present invention, take that to improve the per pass conversion of methyl formate hydrolysis and reduce energy consumption be starting point, proposed a kind of novel method that adopts reaction rectification technique to produce formic acid.
Summary of the invention
The object of the invention is to the deficiency for existing production technology, provide a kind of methyl formate hydrolysis to produce the method for formic acid, the method can effectively be controlled the incidence of reverse esterification, realizes higher one way hydrolysis conversion.
The object of the invention is to be achieved through the following technical solutions: a kind of method that adopts reaction rectification technique to produce formic acid, the method comprises the following steps:
(1) according to production task, require to determine the flow of the fresh methyl-formiate raw material that the unit time need process, by water ester raw materials components mole ratio 2-4:1, calculate the flow of the total raw material water of needs.
(2) fresh methyl-formiate raw material is delivered to after methyl-formiate feed heater is heated to 80-120 ℃ and is sent into reactor by methyl-formiate feedstock pump, raw water is delivered to after raw water well heater is also heated to 80-120 ℃ and is divided into the first rectifying tower raw water and reactor feedstocks water by water transfer pump, and the first rectifying tower raw water and reactor feedstocks water ratio are 0.5-2:1; Reactor feedstocks water is sent into reactor, and the first rectifying tower raw water is sent into the first rectifying tower 3-7 piece theoretical stage place from the top down.
(3) fresh methyl-formiate raw material, subsequent technique circulation are returned circulation methyl-formiate material and reactor feedstocks water issue raw hydrolysis reaction at reactor pressure 0.5-1.5MPa, hydrolysate is delivered to flash tank, and flash tank forms vapor-phase material and liquid phase material heat vaporization at pressure 0.1-0.5MPa, temperature 50-100 ℃ after; Vapor-phase material and liquid phase material are delivered to respectively the first rectifying tower 6-10 and 14-18 piece theoretical stage place from the top down; The first rectifying tower number of theoretical plate is 20-30 piece, and working pressure is 0-0.3MPa, and side line extraction mouth is located at the first rectifying tower 10-14 piece theoretical stage place from the top down; Regulate the flow of a tower reboiler heating steam, control the column bottom temperature 110-160 ℃ of the first rectifying tower, make at the bottom of the tower of the first rectifying tower as 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 the first rectifying tower; In the first rectifying tower, rising steam enters a tower condenser, after condensation, by reflux ratio, is that 1-4 operates; Tower top obtains unhydrolysed methyl-formiate and delivers to circulation methyl-formiate product pump, and the vapor-phase material that methyl alcohol is rich in side line extraction is sent into Second distillation column.
(4) vapor-phase material of the first rectifying tower side line extraction is sent into Second distillation column 10-16 piece theoretical stage place from the top down; Second distillation column number of theoretical plate is 20-30 piece, and working pressure is 0-0.3MPa; Regulate the flow of two tower reboiler heating steams, control the column bottom temperature 70-120 ℃ of Second distillation column, make at the bottom of the tower of Second distillation column as not containing the pure methanol aqueous solution of methyl-formiate; Methanol aqueous solution is discharged at the bottom of the tower of Second distillation column; In Second distillation column, rising steam enters two tower condensers, after condensation, by reflux ratio, be that 1-4 operates, the methyl-formiate that the first rectifying tower side line is taken out of and the methyl-formiate that resterification generates in Second distillation column are delivered to circulation methyl-formiate product pump from the tower top of Second distillation column, the unhydrolysed methyl-formiate obtaining with the first rectifying tower tower top mixes, and forms circulation methyl-formiate material.
(5) methyl-formiate that circulation methyl-formiate product pump is sent the first rectifying tower and Second distillation column tower top here is delivered to after circulation methyl-formiate heating material device is heated to 80-120 ℃ and is sent into reactor, be blended in reactor pressure 0.5-1.5MPa with reactor feedstocks water and fresh methyl-formiate raw material and issue raw hydrolysis reaction, hydrolysate is delivered to flash tank.
Beneficial effect of the present invention is:
(1) technique of the present invention is simple, and the formic acid of one of hydrolysate is from extraction at the bottom of the first rectifying tower, and another product methyl alcohol is all from extraction at the bottom of Second distillation column.
(2) material of two rectifying tower top extraction of the present invention does not need to carry out the separated again of methyl-formiate and methyl alcohol, can direct cycle to reactor and participate in reaction, and in material, contained a small amount of methyl alcohol can make reaction carry out in homogeneous liquid phase, can improve hydrolysis rate.
(3) resterification that the present invention suppresses in rectifying tower by side line extraction methyl alcohol reacts, and 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 whole system.Calculating shows, adopts the present invention to compare with current technique and can save energy 20-30% left and right.
(4) the present invention is easy to operate, and the proportioning raw materials of reactor can be grasped flexibly, is easy to carry out serialization scale operation.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention;
In 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 heating material device 9, reactor 10, flash tank 11, the first rectifying tower 12, one tower condenser 13, one tower reboiler 14, side line extraction material 15, Second distillation column 16, two tower condensers 17, two tower reboilers 18, one 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, comprises the following steps:
1. according to production task, require to determine the flow of the fresh methyl-formiate raw material 1 that the unit time need process, by water ester raw materials components mole ratio 2-4:1, calculate the flow of the total raw material water 2 of needs.
2. fresh methyl-formiate raw material 1 is delivered to after methyl-formiate feed heater 7 is heated to 80-120 ℃ and is sent into reactor 10 by methyl-formiate feedstock pump 4, raw water 2 delivers to by water transfer pump 5 that after raw water well heater 8 is also heated to 80-120 ℃, to be divided into the first rectifying tower raw water 22 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 10, the first rectifying tower raw waters 22 and is sent into the first rectifying tower 12 3-7 piece theoretical stage place from the top down.
3. fresh methyl-formiate raw material 1, subsequent technique circulation are returned circulation methyl-formiate material 3 and reactor feedstocks water 21 issue raw hydrolysis reaction at reactor pressure 0.5-1.5MPa, hydrolysate is delivered to flash tank 11, and flash tank 11 forms vapor-phase material 23 and liquid phase material 24 heat vaporization at pressure 0.1-0.5MPa, temperature 50-100 ℃ after; Vapor-phase material 23 and liquid phase material 24 are delivered to respectively the first rectifying tower 12 6-10 and 14-18 piece theoretical stage place from the top down; The first rectifying tower 12 number of theoretical plates are 20-30 piece, and working pressure is 0-0.3MPa, and side line extraction mouth is located at the first rectifying tower 12 10-14 piece theoretical stage place from the top down; Regulate the flow of tower reboiler 14 heating steams, control the column bottom temperature 110-160 ℃ of the first rectifying tower 12, make at the bottom of the tower of the first rectifying tower 12 as 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 the first rectifying tower 12; The interior rising steam of the first rectifying tower 12 enters a tower condenser 13, after condensation, by reflux ratio, is that 1-4 operates; Tower top 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 side line extraction is sent into Second distillation column 16.
4. the vapor-phase material 15 of the first rectifying tower 12 side line extraction is sent into Second distillation column 16 10-16 piece theoretical stage place from the top down; Second distillation column 16 number of theoretical plates are 20-30 piece, and working pressure is 0-0.3MPa; Regulate the flow of two tower reboiler 18 heating steams, control the column bottom temperature 70-120 ℃ of Second distillation column 16, make at the bottom of the tower of Second distillation column 16 as not containing the pure methanol aqueous solution of methyl-formiate; Methanol aqueous solution is discharged at the bottom of the tower of Second distillation column 16; The interior rising steam of Second distillation column 16 enters two tower condensers 17, after condensation, by reflux ratio, be that 1-4 operates, the methyl-formiate that the first rectifying tower 12 side lines are taken out of and the methyl-formiate that resterification generates in Second distillation column 16 are delivered to circulation methyl-formiate product pump 6 from the tower top of Second distillation column 16, the unhydrolysed methyl-formiate obtaining with the first rectifying tower 12 tower tops mixes, and forms circulation methyl-formiate material 3.
5. the methyl-formiate that circulation methyl-formiate product pump 6 is sent the first rectifying tower 12 and Second distillation column 16 tower tops here is delivered to after circulation methyl-formiate heating material device 9 is heated to 80-120 ℃ and is sent into reactor 10, be blended in reactor pressure 0.5-1.5MPa with reactor feedstocks water 21 and fresh methyl-formiate raw material 1 and issue raw hydrolysis reaction, hydrolysate is delivered to flash tank 11.
In the present invention, reactor 10 can be for take the tubular type homogeneous reactor that formic acid is autocatalysis agent, flash tank 11 can be the common heating evaporating pot of jacketed, coil pipe or shell and tube, and the first rectifying tower 12 and Second distillation column 16 can be all conventional tray column or packing tower.
From the material of the first rectifying tower 12 side line extraction, can be vapour phase, can be also liquid phase, is preferably vapour phase.The vapour phase of side line extraction can directly enter Second distillation column 16, also can after condensation liquefaction, enter Second distillation column 16 again.
From the aqueous formic acid obtaining at the bottom of the first rectifying tower 12 towers, formic acid content is 55-70wt%, and all the other are water; In side line extraction material, containing methanol content, be 50-70wt%, formic acid content is 0.5-2.5wt%, and methyl-formiate content is 15-35wt%, and all the other are water; In the methanol aqueous solution obtaining at the bottom of Second distillation column 16 towers, methanol content is 65-85wt%, and all the other are water.
In the present invention, the vapor-phase material 23 that reaction product forms after the interior heating of flash tank 11 vaporization and liquid phase material 24 are respectively from middle and upper part and the middle and lower part charging of the first rectifying tower 12; For 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 by the material in methyl alcohol enrichment region in good time from extraction in tower, will make in tower methanol content in each column plate liquid phase greatly decline, be conducive to facilitation of hydrolysis; In addition,, because the first rectifying tower top adds again the first supplementary rectifying tower raw water 22, the further hydrolysis of methyl-formiate will be more conducive to impel; Near inrichment due to methyl alcohol Dan extraction district may cause, in this place's tower, reverse esterification occurs; Applicant finds through great many of experiments, is rich in the vapor-phase material of methyl alcohol by side line extraction, and in whole tower, percent hydrolysis can significantly be greater than resterification rate, and net effect is that in tower, hydrolysis reaction is more preponderated.
In order to prevent that the material of extraction from containing more formic acid, can make side line extraction material is vapour phase; But nonetheless in material, still can contain a small amount of formic acid, cause formic acid can not be all from extraction at the bottom of the first rectifying tower; In order to simplify follow-up separation process, in Second distillation column 16 by a small amount of formic acid of bringing into and methyl alcohol generation esterification regeneration methyl-formiate, the methyl-formiate of self bringing into together with side line material steams Returning reactor from the tower top of Second distillation column 16, at the bottom of the tower of Second distillation column 16, can obtain the methanol aqueous solution that does not contain formic acid.
According to described technique, adopt one way hydrolysis conversion of the present invention can reach 40-55%, be better than current traditional technology one way hydrolysis conversion not higher than 20% level.
Below by specific embodiment, the invention will be further described, but the present invention should be interpreted as and be only applicable to following case.
Embodiment 1
As shown in Figure 1, the water that flow is 3180kg/h is pressurized to 0.8MPa(gauge pressure through water transfer pump 5) after send into raw water well heater 8 and be heated to 100 ℃, be split into the first rectifying tower raw water 22(1590kg/h) with reactor feedstocks water 21(1590kg/h).Flow is that the fresh methyl-formiate raw material of 4140kg/h (is 98.5% containing methyl-formiate, formic acid 0.5%, water 1.0%) through methyl-formiate feedstock pump 4, be pressurized to 0.8MPa(gauge pressure) after send into methyl-formiate feed heater 7 and be heated to 100 ℃ and enter reactor 10, the material that reactor is discharged enters flash tank 11, flash tank 11 is in pressure 0.12MPa(gauge pressure), vaporization at temperature 60-65 ℃, vapor-phase material 23 and liquid phase material 24 enter respectively the first rectifying tower the 6th and the 14th theoretical stage place (the total theoretical stage of this tower is 20) from the top down, the first rectifying tower raw water 22 enters this tower the 3rd theoretical stage place from the top down.
At the 10th block of theoretical stage place vapour phase extraction material 15 of the first rectifying tower 12, enter the 10th theoretical stage (the total theoretical stage of this tower is 20) of Second distillation column 16.The circulation methyl-formiate material 3 of two overhead extractions is pressurized to 0.8MPa(gauge pressure by circulation methyl-formiate product pump 6) deliver to after circulation methyl-formiate heating material device 9 is heated to 100 ℃ and send into reactor 10.
The first rectifying tower 12 tower top pressures are 0.11MPa(gauge pressure), temperature is 54.9 ℃, reflux ratio is 2.5; Second distillation column 16 tower top pressures are 0.1MPa(gauge pressure), temperature is 53.3 ℃, reflux ratio is 3.5; After stable operation, obtaining circulation methyl-formiate material 3 flows is 5987kg/h, at the bottom of the first rectifying tower, obtaining mass flow is 4687kg/h(formic acid content 67.1wt%), temperature is 133-138 ℃, at the bottom of Second distillation column, obtaining mass flow is 2633kg/h(methanol content 82.6wt%), temperature is 86-91 ℃.
According to 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 obtain the total hydrolysis conversion of one way is 43.1%.
Embodiment 2
As shown in Figure 1, the water that flow is 3670kg/h is pressurized to 0.6MPa(gauge pressure through water transfer pump 5) after send into raw water well heater 8 and be heated to 80 ℃, be split into the first rectifying tower raw water 22(1835kg/h) with reactor feedstocks water 21(1835kg/h).Flow is that the fresh methyl-formiate raw material of 4140kg/h (is 98.5% containing methyl-formiate, formic acid 0.5%, water 1.0%) through methyl-formiate feedstock pump 4, be pressurized to 0.6MPa(gauge pressure) after send into methyl-formiate feed heater 7 and be heated to 80 ℃ and enter reactor 10, the material that reactor is discharged enters flash tank 11, flash tank 11 is in pressure 0.12MPa(gauge pressure), vaporization at temperature 60-65 ℃, vapor-phase material 23 and liquid phase material 24 enter respectively the first rectifying tower the 6th and the 14th theoretical stage place (the total theoretical stage of this tower is 20) from the top down, the first rectifying tower raw water 22 enters this tower the 3rd theoretical stage place from the top down.
At the 10th block of theoretical stage place vapour phase extraction material 15 of the first rectifying tower 12, enter the 13rd theoretical stage (the total theoretical stage of this tower is 25) of Second distillation column 16.The circulation methyl-formiate material 3 of two overhead extractions is pressurized to 0.6MPa(gauge pressure by circulation methyl-formiate product pump 6) deliver to after circulation methyl-formiate heating material device 9 is heated to 80 ℃ and send into reactor 10.
The first rectifying tower 12 tower top pressures are 0.11MPa(gauge pressure), temperature is 55.4 ℃, reflux ratio is 2.5; Second distillation column 16 tower top pressures are 0.1MPa(gauge pressure), temperature is 53.3 ℃, reflux ratio is 3.5; After stable operation, obtaining circulation methyl-formiate material 3 flows is 5192kg/h, at the bottom of the first rectifying tower, obtaining mass flow is 5040kg/h(formic acid content 62.4wt%), temperature is 131-136 ℃, at the bottom of Second distillation column, obtaining mass flow is 2770kg/h(methanol content 78.5wt%), temperature is 89-94 ℃.
According to 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 obtain the total hydrolysis conversion of one way is 46.6%.
Embodiment 3
As shown in Figure 1, the water that flow is 3670kg/h is pressurized to 1.2MPa(gauge pressure through water transfer pump 5) after send into raw water well heater 8 and be heated to 120 ℃, be split into the first rectifying tower raw water 22(1835kg/h) with reactor feedstocks water 21(1835kg/h).Flow is that the fresh methyl-formiate raw material of 4140kg/h (is 98.5% containing methyl-formiate, formic acid 0.5%, water 1.0%) through methyl-formiate feedstock pump 4, be pressurized to 1.2MPa(gauge pressure) after send into methyl-formiate feed heater 7 and be heated to 120 ℃ and enter reactor 10, the material that reactor is discharged enters flash tank 11, flash tank 11 is in pressure 0.22MPa(gauge pressure), vaporization at temperature 73-78 ℃, vapor-phase material 23 and liquid phase material 24 enter respectively the first rectifying tower the 10th and the 18th theoretical stage place (the total theoretical stage of this tower is 30) from the top down, the first rectifying tower raw water 22 enters this tower the 6th theoretical stage place from the top down.
At the 14th block of theoretical stage place vapour phase extraction material 15 of the first rectifying tower 12, enter the 15th theoretical stage (the total theoretical stage of this tower is 30) of Second distillation column 16.The circulation methyl-formiate material 3 of two overhead extractions is pressurized to 1.2MPa(gauge pressure by circulation methyl-formiate product pump 6) deliver to after circulation methyl-formiate heating material device 9 is heated to 120 ℃ and send into reactor 10.
The first rectifying tower 12 tower top pressures are 0.21MPa(gauge pressure), temperature is 68.8 ℃, reflux ratio is 2; Second distillation column 16 tower top pressures are 0.2MPa(gauge pressure), temperature is 66.5 ℃, reflux ratio is 2; After stable operation, obtaining circulation methyl-formiate material 3 flows is 4735kg/h, at the bottom of the first rectifying tower, obtaining mass flow is 5043kg/h(formic acid content 62.4wt%), temperature is 142-147 ℃, at the bottom of Second distillation column, obtaining mass flow is 2767kg/h(methanol content 78.6wt%), temperature is 105-110 ℃.
According to 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 obtain the total hydrolysis conversion of one way is 48.9%.
Embodiment 4
As shown in Figure 1, the water that flow is 4282kg/h is pressurized to 0.8MPa(gauge pressure through water transfer pump 5) after send into raw water well heater 8 and be heated to 100 ℃, be split into the first rectifying tower raw water 22(1427kg/h) with reactor feedstocks water 21(2855kg/h).Flow is that the fresh methyl-formiate raw material of 4140kg/h (is 98.5% containing methyl-formiate, formic acid 0.5%, water 1.0%) through methyl-formiate feedstock pump 4, be pressurized to 0.8MPa(gauge pressure) after send into methyl-formiate feed heater 7 and be heated to 100 ℃ and enter reactor 10, the material that reactor is discharged enters flash tank 11, flash tank 11 is in pressure 0.12MPa(gauge pressure), vaporization at temperature 63-68 ℃, vapor-phase material 23 and liquid phase material 24 enter respectively the first rectifying tower the 8th and the 16th theoretical stage place (the total theoretical stage of this tower is 25) from the top down, the first rectifying tower raw water 22 enters this tower the 4th theoretical stage place from the top down.
At the 12nd block of theoretical stage place vapour phase extraction material 15 of the first rectifying tower 12, enter the 13rd theoretical stage (the total theoretical stage of this tower is 25) of Second distillation column 16.The circulation methyl-formiate material 3 of two overhead extractions is pressurized to 0.8MPa(gauge pressure by circulation methyl-formiate product pump 6) deliver to after circulation methyl-formiate heating material device 9 is heated to 100 ℃ and send into reactor 10.
The first rectifying tower 12 tower top pressures are 0.11MPa(gauge pressure), temperature is 55.8 ℃, reflux ratio is 2.5; Second distillation column 16 tower top pressures are 0.1MPa(gauge pressure), temperature is 53.5 ℃, reflux ratio is 3; After stable operation, obtaining circulation methyl-formiate material 3 flows is 5353kg/h, at the bottom of the first rectifying tower, obtaining mass flow is 5319kg/h(formic acid content 59.2wt%), temperature is 130-135 ℃, at the bottom of Second distillation column, obtaining mass flow is 3103kg/h(methanol content 70.1wt%), temperature is 92-97 ℃.
According to 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 obtain the total hydrolysis conversion of one way is 46.4%.
Embodiment 5
As shown in Figure 1, the water that flow is 4282kg/h is pressurized to 0.8MPa(gauge pressure through water transfer pump 5) after send into raw water well heater 8 and be heated to 100 ℃, be split into the first rectifying tower raw water 22(2855kg/h) with reactor feedstocks water 21(1427kg/h).Flow is that the fresh methyl-formiate raw material of 4140kg/h (is 98.5% containing methyl-formiate, formic acid 0.5%, water 1.0%) through methyl-formiate feedstock pump 4, be pressurized to 0.8MPa(gauge pressure) after send into methyl-formiate feed heater 7 and be heated to 100 ℃ and enter reactor 10, the material that reactor is discharged enters flash tank 11, flash tank 11 is in pressure 0.22MPa(gauge pressure), vaporization at temperature 75-80 ℃, vapor-phase material 23 and liquid phase material 24 enter respectively the first rectifying tower the 8th and the 16th theoretical stage place (the total theoretical stage of this tower is 25) from the top down, the first rectifying tower raw water 22 enters this tower the 4th theoretical stage place from the top down.
At the 12nd block of theoretical stage place vapour phase extraction material 15 of the first rectifying tower 12, enter the 13rd theoretical stage (the total theoretical stage of this tower is 25) of Second distillation column 16.The circulation methyl-formiate material 3 of two overhead extractions is pressurized to 0.8MPa(gauge pressure by circulation methyl-formiate product pump 6) deliver to after circulation methyl-formiate heating material device 9 is heated to 100 ℃ and send into reactor 10.
The first rectifying tower 12 tower top pressures are 0.21MPa(gauge pressure), temperature is 70.5 ℃, reflux ratio is 3.5; Second distillation column 16 tower top pressures are 0.2MPa(gauge pressure), temperature is 67.7 ℃, reflux ratio is 3.5; After stable operation, obtaining circulation methyl-formiate material 3 flows is 4105kg/h, at the bottom of the first rectifying tower, obtaining mass flow is 5288kg/h(formic acid content 59.5wt%), temperature is 141-146 ℃, at the bottom of Second distillation column, obtaining mass flow is 3134kg/h(methanol content 69.4wt%), temperature is 108-113 ℃.
According to 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 obtain the total hydrolysis conversion of one way is 53.6%.
Claims (4)
1. the methyl-formiate of take is produced a method for formic acid as raw material adopts reaction rectification technique, it is characterized in that, the method comprises the following steps:
(1) according to production task, require to determine the flow of the fresh methyl-formiate raw material that the unit time need process, by water ester raw materials components mole ratio 2-4:1, calculate the flow of the total raw material water of needs;
(2) fresh methyl-formiate raw material is delivered to after methyl-formiate feed heater is heated to 80-120 ℃ and is sent into reactor by methyl-formiate feedstock pump, raw water is delivered to after raw water well heater is also heated to 80-120 ℃ and is divided into the first rectifying tower raw water and reactor feedstocks water by water transfer pump, and the first rectifying tower raw water and reactor feedstocks water ratio are 0.5-2:1; Reactor feedstocks water is sent into reactor, and the first rectifying tower raw water is sent into the first rectifying tower 3-7 piece theoretical stage place from the top down;
(3) fresh methyl-formiate raw material, subsequent technique circulation are returned circulation methyl-formiate material and reactor feedstocks water issue raw hydrolysis reaction at reactor pressure 0.5-1.5MPa, hydrolysate is delivered to flash tank, and flash tank forms vapor-phase material and liquid phase material heat vaporization at pressure 0.1-0.5MPa, temperature 50-100 ℃ after; Vapor-phase material and liquid phase material are delivered to respectively the first rectifying tower 6-10 and 14-18 piece theoretical stage place from the top down; The first rectifying tower number of theoretical plate is 20-30 piece, and working pressure is 0-0.3MPa, and side line extraction mouth is located at the first rectifying tower 10-14 piece theoretical stage place from the top down; Regulate the flow of a tower reboiler heating steam, control the column bottom temperature 110-160 ℃ of the first rectifying tower, make at the bottom of the tower of the first rectifying tower as 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 the first rectifying tower; In the first rectifying tower, rising steam enters a tower condenser, after condensation, by reflux ratio, is that 1-4 operates; Tower top obtains unhydrolysed methyl-formiate and delivers to circulation methyl-formiate product pump, and the vapor-phase material that methyl alcohol is rich in side line extraction is sent into Second distillation column;
(4) vapor-phase material of the first rectifying tower side line extraction is sent into Second distillation column 10-16 piece theoretical stage place from the top down; Second distillation column number of theoretical plate is 20-30 piece, and working pressure is 0-0.3MPa; Regulate the flow of two tower reboiler heating steams, control the column bottom temperature 70-120 ℃ of Second distillation column, make at the bottom of the tower of Second distillation column as not containing the pure methanol aqueous solution of methyl-formiate; Methanol aqueous solution is discharged at the bottom of the tower of Second distillation column; In Second distillation column, rising steam enters two tower condensers, after condensation, by reflux ratio, be that 1-4 operates, the methyl-formiate that the first rectifying tower side line is taken out of and the methyl-formiate that resterification generates in Second distillation column are delivered to circulation methyl-formiate product pump from the tower top of Second distillation column, the unhydrolysed methyl-formiate obtaining with the first rectifying tower tower top mixes, and forms circulation methyl-formiate material;
(5) the circulation methyl-formiate material that circulation methyl-formiate product pump is sent the first rectifying tower and Second distillation column tower top here is delivered to after circulation methyl-formiate heating material device is heated to 80-120 ℃ and is sent into reactor, be blended in reactor pressure 0.5-1.5MPa with reactor feedstocks water and fresh methyl-formiate raw material and issue raw hydrolysis reaction, hydrolysate is delivered to flash tank.
2. adopt according to claim 1 reaction rectification technique to produce the method for formic acid, it is characterized in that, reactor is for take the tubular type homogeneous reactor that formic acid is autocatalysis agent, flash tank is the common heating evaporating pot of jacketed, coil pipe or shell and tube, and the first rectifying tower and Second distillation column are conventional tray column or packing tower.
3. adopting according to claim 1 reaction rectification technique to produce the method for formic acid, it is characterized in that, is vapour phase or liquid phase from the material of the first rectifying tower side line extraction; The vapour phase of side line extraction directly enters Second distillation column, or enters Second distillation column after condensation liquefaction again.
4. adopting according to claim 1 reaction rectification technique to produce the method for formic acid, it is characterized in that, is vapour phase from the material of the first rectifying tower side line extraction.
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| 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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| 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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| Title |
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| 甲酸甲酯水解工艺的研究;陈云华等;《云南化工》;20000430;第27卷(第2期);3-5 * |
| 陈云华等.甲酸甲酯水解工艺的研究.《云南化工》.2000,第27卷(第2期),3-5. |
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