CN102399130B - Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid - Google Patents
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 135
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000000895 extractive distillation Methods 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 67
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 67
- 229920002554 vinyl polymer Polymers 0.000 claims description 67
- 229960004756 ethanol Drugs 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 238000000605 extraction Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 31
- 230000032050 esterification Effects 0.000 claims description 30
- 238000005886 esterification reaction Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 22
- 239000002351 wastewater Substances 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- -1 silicon ester Chemical class 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 11
- 235000019439 ethyl acetate Nutrition 0.000 abstract 4
- 239000002994 raw material Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000003809 water extraction Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- UPUANNBILBRCST-UHFFFAOYSA-N ethanol;ethene Chemical compound C=C.CCO UPUANNBILBRCST-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
The invention discloses a method for simplifying a rectification process for preparing ethanol through hydrogenation of acetic acid. An extractive distillation mode is adopted, and an ethanol product with higher purity can be obtained; a rectifying device can meet the separation requirement on an acetic ether product and an ethanol product; in addition, the acetic ether and the ethanol are separated by the same separation equipment; when the ethanol is produced, crude acetic ether and absolute ethanol products are obtained in the device, and when the ethanol is not produced, the device can produce the qualified acetic ether product, so that the device investment is saved.
Description
Technical field
The present invention relates to the product purification of organic chemistry industry, be specially the method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid.
Background technology
Ethanol, is commonly called as alcohol, and it is a kind of inflammable, volatile colourless transparent liquid under normal temperature, normal pressure, and its aqueous solution has special, pleasant fragrance, and slightly with irritating.Having many uses of ethanol, can manufacture acetic acid, beverage, essence, dyestuff, fuel etc. with ethanol.The ethanol that in medical treatment, also conventional volume fraction is 70%-75% is made sterilizing agent etc.
Industrial generally with amylo process or the direct aquation method of ethene ethanol production:
1. fermentation method
Fermentation legal system ethanol is to grow up on the basis of wine brewing, within the quite long period of history, is once unique commercial run of producing ethanol.The raw material of fermentation method can be amyloid agricultural-food, as cereal, potato class or wild plant fruit etc.; Also can use the waste molasses of sugar refinery; Or with wood chip, the plant haulm etc. of cellulose.These materials, after certain pre-treatment, through hydrolysis (making raw material without this step with molasses sugar), ferment, can make ethanol.
Massfraction in fermented liquid is about 6% ~ 10%, and contains some other organic impurity, can obtain 95% industrial alcohol through rectifying.
2. ethene aquation method
The direct aquation method of ethene, under the condition that heats, pressurizes and have catalyzer to exist, is ethene and water direct reaction exactly, produces ethanol:
CH
2═ CH
2+ H-OH → C
2h
5this reaction of OH(is carried out in two steps, and the first step is in water-tetrahydrofuran solution, to generate organomercury compound with mercury salts such as mercuric acetates, then uses sodium borohydride reduction).
Raw material-ethene in this method can be taken from oil gas in a large number, and cost is low, and output is large, can save so a large amount of grain, and therefore development is very fast.
Southwest Chemical Research and Design Institute has been invented a kind of method (CN 201010584928.0) of vinyl acetic monomer Hydrogenation for ethanol of using simultaneously, the method adopts vinyl acetic monomer or ritalin as raw material, under copper-based catalysts effect, hydrogenation generates ethanol, present method has been invented the production process route that is made ethanol by coal as raw material, current China coal methyl alcohol processed and downstream acetic acid production capacity surplus are solved, the problem of downstream application deficiency.Also solved because China's ethene is in short supply simultaneously, grain is in short supply causes the situation that ethanol is under-supply.
The raw material vinyl acetic monomer that CN 201010584928.0 prepares ethanol adopts acetic acid and alcohols esterification under the katalysis of sulfuric acid to obtain conventionally, and the method that vinyl acetic monomer technique is produced in conventional esterification needs 5 towers to separate is conventionally carried out rectification and purification and finally just can be obtained qualified vinyl acetic monomer product.The product of (seeing accompanying drawing 1) reaction is ethane and the water that the ethanol that generates of main reaction and side reaction generate, and goes out in the material of reactor simultaneously and also comprises the vinyl acetic monomer that unreacted is complete, also needs further to refine so will obtain qualified alcohol product.
Alcohol product is divided into different specifications, comprising industrial alcohol (96% percent by volume), the different sizes such as chemical reagent (95% percent by volume), dehydrated alcohol (99.5 ~ 99.8% mass percent), adopt different process for purification for different product needed.
Summary of the invention
It is 90% the thick product of vinyl acetic monomer that the raw material vinyl acetic monomer of preparing ethanol due to CN 201010584928.0 can use content, so the consideration that the present invention is based on and save investment, reduces energy consumption, simple flow, has invented the technique that a kind of vinyl acetic monomer preparation of ethanol by hydrogenating rectifying is simplified.
Above-mentioned purpose of the present invention is achieved by the following technical solution: a kind of method of vinyl acetic monomer simplifying rectification process for preparing ethanol through hydrogenation, comprises the steps:
1) feed ethanol and acetic acid add from esterification column tower reactor, under the sulfuric acid catalysis effect circulating, react in tower reactor;
2) by esterification column Reaction Separation, obtain the thick product of hydrogenating materials vinyl acetic monomer, for hydrogenation process reaction, the water that esterification generates returns to ester wherein and alcohol recovery to esterification column by waste water reclamation tower and again reacts;
3) step 2 is obtained to the thick product of vinyl acetic monomer and carry out hydrogenation reaction by catalyzer, hydrogenator outlet material carries out cooling, looping back hydrogenator entrance by the complete hydrogen of unreacted after vapor-liquid separation and a small amount of organic constituent again reuses, the concentration tower tower middle part of liquid phase material from vinyl acetic monomer Production Flow Chart enters, after ethylene glycol separation of extractive distillation, the vinyl acetic monomer that overhead extraction unreacted is complete and a small amount of ethanol, tower reactor material enters into the low ester recovery tower of vinyl acetic monomer Production Flow Chart, remove the water in material by the method for ethylene glycol extracting rectifying, final tower top obtains dehydrated alcohol product,
4) the tower reactor material in step 3 is again by after the treating tower rectifying separation in vinyl acetic monomer Production Flow Chart, and the ethylene glycol that tower reactor obtains turns back to concentration tower and low ester recovery tower recycles.
In the present invention, the content >=90%(wt% of vinyl acetic monomer in the thick product that step 2 obtains), preferably vinyl acetic monomer content is 90.0%-92.0%.
In the present invention, the catalyzer that step 3 adopts be in preferred CN 201010584928.0 preparation catalyzer, specifically, preferably copper is catalyst based, its take Cu as active ingredient, with SiO
2for carrier, take transition metal or/and at least one in basic metal is auxiliary agent.Further, described transition metal is at least one in Zn, Mn, Mo, Co, and described basic metal is at least one in Mg, Ba, and described carrier derives from least one in silicate, silicon sol, silicon ester.Described active component content is 5～50% of vehicle weight, and auxiliary agent content is vehicle weight 1%～10%.
In the present invention, dehydrated alcohol product content >=99.5%(mass percent that step 3 obtains).
Compared with prior art, beneficial effect of the present invention is:
(1), adopt the mode of extracting rectifying, allow to obtain the alcohol product that purity is higher;
(2), rectifier unit can meet the separation requirement of producing vinyl acetic monomer product and alcohol product;
(3), vinyl acetic monomer separates and separation of ethanol shares separating device, obtains thick vinyl acetic monomer and dehydrated alcohol product at alcohol production timer, can produce qualified vinyl acetic monomer product at ethanol stopping production timer, economizer investment.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of production ethyl acetate of the present invention.
Fig. 2 is the process flow sheet that the present invention produces ethanol.
Wherein, in Fig. 1, D101 is esterification column return tank, and D102 is concentration tower return tank, the low ester recovery tower of D103 return tank, D104 is treating tower return tank, and D105 is waste water reclamation tower return tank, and T101 is esterification column, T102 is concentration tower, T103 is low ester recovery tower, and T104 is treating tower, and T105 is waste water reclamation tower.
In Fig. 2, D201 is esterification column return tank, D202 is vinyl acetic monomer tower return tank, D203 ethanol tower return tank, and D204 is regenerator column return tank, D205 is waste water reclamation tower return tank, T201 is esterification column, and T202 is vinyl acetic monomer tower, and T203 is ethanol tower, T204 is regenerator column, and T205 is waste water reclamation tower.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1:(Figure of description 1)
In the production process of vinyl acetic monomer, feed ethanol and acetic acid add from esterification column tower reactor, under the sulfuric acid catalysis effect circulating in tower reactor, react, reaction product vinyl acetic monomer, water, the a small amount of low ester of by product and complete a small amount of ethanol and the acetic acid of unreacted steam from tower top, layering in esterification column return tank after condensation, and water extraction is processed in waste water reclamation tower, oil phase part is back to esterification tower top, and part extraction is to concentration tower.
Esterification overhead extraction oil phase material is from concentration tower top material inlet, and after rectifying separation, tower reactor extraction has removed the thick product introduction of vinyl acetic monomer of low ester, ethanol and most water and processed in treating tower; Layering in concentration tower return tank after the material condensation that concentrate tower top steams, water extraction is processed in waste water reclamation tower, and oil phase part is back to concentrate tower top, and part extraction is to low ester recovery tower.
Concentrate overhead extraction oil phase material is from low ester recovery tower middle part charging, after rectifying separation, tower reactor extraction turns back to esterification column tower reactor containing the vinyl acetic monomer of ethanol on a small quantity and recycles, tower top steams layering in low ester recovery tower return tank after material condensation, water extraction is processed in waste water reclamation tower, oil phase part is back to low ester and reclaims tower top, and part oil phase arrives out-of-bounds as the low ester extraction of byproduct, and wherein low ester content is 90%-95% (mass percent).
Concentration tower tower reactor extraction material enters at the bottom for the treatment of tower, after rectifying separation, the a small amount of acetic acid of tower reactor extraction and vinyl acetic monomer mixture turn back to esterification column tower reactor and recycle, tower top steams layering in treating tower return tank after material condensation, water extraction is processed in waste water reclamation tower, oil phase part is back to refining tower top, and part oil phase arrives out-of-bounds as the extraction of product vinyl acetic monomer, product vinyl acetic monomer content >=99.5%(mass percent).
From esterification column, concentration tower, low ester recovery tower and treating tower return tank of top of the tower, the water material of extraction enters into waste water reclamation tower rectifying separation, the discharge of wastewater that tower reactor extraction has removed organic constituent arrives out-of-bounds, and the organic constituents such as a small amount of ethanol of overhead extraction, vinyl acetic monomer turn back to esterification column tower reactor and recycle.
Embodiment 2:(Figure of description 2)
In the production process of ethanol, feed ethanol and acetic acid add from esterification column tower reactor, under the sulfuric acid catalysis effect circulating in tower reactor, react, reaction product vinyl acetic monomer, water, the a small amount of low ester of by product and complete a small amount of ethanol and the acetic acid of unreacted steam from tower top, layering in esterification column return tank after condensation, water extraction is processed in waste water reclamation tower, oil phase part is back to esterification tower top, the gasification tower of part extraction vinyl acetic monomer hydrogenation workshop section, the oil phase of extraction is the thick product of vinyl acetic monomer, wherein vinyl acetic monomer content is 90.0%-92.0%(mass percent).
Esterification overhead extraction oil phase material enters into hydrogenation process, and from the charging of gasification tower top, after heating and gasifying, material steam enters into hydrogenator after mixing with hydrogen and reacts, and vinyl acetic monomer hydrogenation generates ethanol.Hydrogenator outlet material, by after cooling, mainly contains the complete hydrogen of unreacted, vinyl acetic monomer and a small amount of ethanol in uncooled gas phase, turn back to hydrogenator import and recycle.In liquid phase material under condensation, mainly contain hydrogenation products ethanol and a small amount of unreacted vinyl acetic monomer and with components such as the water bringing in raw material, liquid phase material enters into ethanol rectification working process and separates.
The liquid phase material of condensation enters from the middle part of vinyl acetic monomer tower, adds ethylene glycol to carry out extracting rectifying on the top of vinyl acetic monomer tower, and after rectifying separation, the water-free vinyl acetic monomer of overhead extraction and a small amount of ethanol, turn back to hydrogenator import and recycle.
The material of vinyl acetic monomer tower tower reactor extraction enters from the middle part of ethanol tower, add ethylene glycol to carry out extracting rectifying on the top of ethanol tower, after rectifying separation, overhead extraction content >=99.5%(mass percent) dehydrated alcohol product, the material of tower reactor extraction mainly contains water and ethylene glycol, enters into regenerator column and processes.
Enter from regenerator column middle part containing water glycol, after separating by rectification under vacuum (working pressure is 30-50kPa), overhead extraction discharge of wastewater is to out-of-bounds, tower reactor extraction content >=99.9%(mass percent) ethylene glycol turn back to vinyl acetic monomer tower and ethanol tower recycles.
In ethanol production process, separating the vinyl acetic monomer tower using is in vinyl acetic monomer production process, to separate the concentration tower using; In ethanol production process, separating the vinyl acetic monomer tower using is in vinyl acetic monomer production process, to separate the low ester recovery tower using; In ethanol production process, separating the regenerator column using is in vinyl acetic monomer production process, to separate the treating tower using.
The processing step of embodiment 1 and condition are referring to table 1
| Process conditions | Processing condition 1 | Processing condition 2 |
| (1) esterification column | ? | ? |
| Vinyl acetic monomer content (wt%) in the thick vinyl acetic monomer of extraction | 90 | 92 |
| Esterification column tower working pressure (kPa) | 100 | 100 |
| Stage number | 50 | 50 |
| (2) concentration tower | ? | ? |
| Vinyl acetic monomer content (wt%) after concentrate | 93 | 94.5 |
| Concentration tower working pressure (kPa) | 100 | 100 |
| Stage number | 50 | 50 |
| (3) low ester recovery tower | ? | ? |
| Reclaim low ester content (wt%) | 92.3 | 93.5 |
| Low ester recovery tower working pressure (kPa) | 100 | 100 |
| Stage number | 40 | 40 |
| (4) treating tower | ? | ? |
| Product vinyl acetic monomer content (wt%) | 99.5 | 99.8 |
| Treating tower working pressure (kPa) | 100 | 100 |
| Stage number | 60 | 60 |
| (5) waste water reclamation tower | ? | ? |
| Waste water content (wt%) | 99.5 | 99.7 |
| Waste water reclamation tower working pressure (kPa) | 100 | 100 |
| Stage number | 50 | 50 |
The processing step of embodiment 2 and condition
| Process conditions | Processing condition 1 | Processing condition 2 |
| (1) esterification column | ? | ? |
| Vinyl acetic monomer content (wt%) in the thick vinyl acetic monomer of extraction | 90 | 92 |
| Esterification column tower working pressure (kPa) | 100 | 100 |
| Stage number | 50 | 50 |
| (2) vinyl acetic monomer tower | ? | ? |
| Ethanol content in raw material charging (wt%) | 92.5 | 93.0 |
| Vinyl acetic monomer content (wt%) in raw material charging | 3.4 | 2.7 |
| Extraction distillation solvent ethylene glycol and raw materials quality ratio | 2 | 3 |
| Overhead extraction vinyl acetic monomer content (wt%) | 46.0 | 57.5 |
| Vinyl acetic monomer tower working pressure (kPa) | 100 | 100 |
| Stage number | 50 | 50 |
| Extraction distillation solvent ethylene glycol feed tray number | 4 | 5 |
| Raw material feed tray number | 23 | 25 |
| (3) ethanol tower | ? | ? |
| Extraction distillation solvent ethylene glycol and raw materials quality ratio | 2 | 2.5 |
| Product dehydrated alcohol content (wt%) | 99.5 | 99.8 |
| Ethanol tower working pressure (kPa) | 100 | 100 |
| Stage number | 40 | 40 |
| Extraction distillation solvent ethylene glycol feed tray number | 4 | 5 |
| Raw material feed tray number | 20 | 23 |
| (4) regenerator column | ? | ? |
| Regenerated solvent ethylene glycol content (wt%) | 99.9 | 99.95 |
| Regenerator column working pressure (kPa) | 50 | 35 |
| Stage number | 60 | 60 |
| (5) waste water reclamation tower | ? | ? |
| Waste water content (wt%) | 99.5 | 99.7 |
| Waste water reclamation tower working pressure (kPa) | 100 | 100 |
| Stage number | 50 | 50 |
Claims (4)
1. a method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid, comprises the steps:
1) feed ethanol and acetic acid add from esterification column tower reactor, under the sulfuric acid catalysis effect circulating, react in tower reactor;
2) by esterification column Reaction Separation, obtain the thick product of hydrogenating materials vinyl acetic monomer, for hydrogenation process reaction, the water that esterification generates returns to ester wherein and alcohol recovery to esterification column by waste water reclamation tower and again reacts;
3) step 2 is obtained to the thick product of vinyl acetic monomer and carry out hydrogenation reaction by catalyzer, hydrogenator outlet material carries out cooling, looping back hydrogenator entrance by the complete hydrogen of unreacted after vapor-liquid separation and a small amount of organic constituent again reuses, the concentration tower tower middle part of liquid phase material from vinyl acetic monomer Production Flow Chart enters, after ethylene glycol separation of extractive distillation, the vinyl acetic monomer that overhead extraction unreacted is complete and a small amount of ethanol, tower reactor material enters into the low ester recovery tower of vinyl acetic monomer Production Flow Chart, remove the water in material by the method for ethylene glycol extracting rectifying, final tower top obtains dehydrated alcohol product, described catalyzer copper is catalyst based, its take Cu as active ingredient, with SiO
2for carrier, take transition metal or/and at least one in basic metal is auxiliary agent, described transition metal is at least one in Zn, Mn, Mo, Co, and described basic metal is at least one in Mg, Ba, and described carrier derives from least one in silicate, silicon sol, silicon ester, described active component content is 5～50% of vehicle weight, and auxiliary agent content is vehicle weight 1%～10%,
4) the tower reactor material in step 3 is again by after the treating tower rectifying separation in vinyl acetic monomer Production Flow Chart, and the ethylene glycol that tower reactor obtains turns back to concentration tower and low ester recovery tower recycles.
2. the method for claim 1, the content >=90 wt % of vinyl acetic monomer in the thick product that wherein step 2 obtains.
3. the method for claim 1, in the thick product that wherein step 2 obtains, the content of vinyl acetic monomer is 90.0 wt %-92.0 wt %.
4. the method as described in claim 1-3 any one, dehydrated alcohol product content mass percent >=99.5% that wherein step 3 obtains.
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| CN102718627B (en) * | 2012-06-25 | 2014-06-18 | 西安隽通电子设备有限公司 | Preparation method of ethanol by adding hydrogen to ethyl acetate |
| CN102757308B (en) * | 2012-07-03 | 2015-06-10 | 张锋新 | Method of preparing high-purity ethanol |
| CN103894206B (en) * | 2012-12-27 | 2016-09-07 | 中国石油化工股份有限公司 | High activity copper-based catalysts, preparation method and its usage |
| CN104043484B (en) * | 2013-03-13 | 2016-10-12 | 中国石油天然气股份有限公司 | Catalyst for preparing ethanol by catalytic hydrogenation of acetic acid and preparation and application thereof |
| CN104211575A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Method for preparation of ethanol by direct hydrogenation of acetic acid |
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