CN105218309A - Produce the method for ethylene glycol - Google Patents
Produce the method for ethylene glycol Download PDFInfo
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- CN105218309A CN105218309A CN201410314188.7A CN201410314188A CN105218309A CN 105218309 A CN105218309 A CN 105218309A CN 201410314188 A CN201410314188 A CN 201410314188A CN 105218309 A CN105218309 A CN 105218309A
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- dimethyl oxalate
- ethylene glycol
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- logistics
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 238000000034 method Methods 0.000 title claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 131
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000011084 recovery Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- -1 nitrous acid ester Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method of producing ethylene glycol, mainly solve prior art and there is technical process complexity, dimethyl oxalate Crystallization Plugging e-quipment and pipe, material consumption and the high problem of energy consumption.The present invention is comprised the following steps by employing: gas raw material a) containing CO and methyl nitrite enters coupler reactor, obtains the logistics containing dimethyl oxalate after reaction; B) the described logistics containing dimethyl oxalate does not cool and directly enters dimethyl oxalate recovery tower, the logistics comprising methyl alcohol enters and the described gaseous stream counter current contact containing dimethyl oxalate from dimethyl oxalate recovery tower tower top, tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product stream; C) described dimethyl oxalate product stream enters hydrogenator, obtains the logistics containing ethylene glycol after reaction; D) the described technical scheme containing obtaining product ethylene glycol after the stream purification of ethylene glycol solves this problem preferably, can be used in the industrial production of ethylene glycol.
Description
Technical field
The present invention relates to a kind of method of producing ethylene glycol, specifically, produce the method for ethylene glycol through dimethyl oxalate two-step approach with coal based synthetic gas.
Background technology
Ethylene glycol (EG), as a kind of important Organic Chemicals, is widely used in producing the industries such as trevira, frostproofer, lubricant.Synthesizing glycol has kinds of processes route, is industrially at present mainly oil ethene route.Along with the day by day scarcity of petroleum resources, more and more come into one's own by the exploitation of coal based synthetic gas preparing ethylene glycol operational path.
Two steps are divided into: CO oxidative coupling synthesizing dimethyl oxalate and dimethyl oxalate shortening preparing ethylene glycol by synthetic gas indirect synthesis ethylene glycol.Dimethyl oxalate (DMO) is important intermediates.The synthetic route of DMO mainly contains two: Article 1 route generates by methyl alcohol and oxalic acid esterification, there is waste discharge amount large, the shortcoming that environmental pollution is serious; Another route is that linked reaction under palladium system or platinum group catalyst generates by CO and methyl nitrite.Because Developing Coal Chemical Industry is in recent years rapid, Article 2 route causes the extensive concern of especially Chinese researcher and enterprise both at home and abroad through the intermediate steps of synthetic gas preparing ethylene glycol as coal, CO is at loading type Pd/α-Al
2o
3under catalyst action, generate DMO and NO with methyl nitrite linked reaction under normal pressure, main reaction equation is as follows:
2CO+2CH
3ONO→(COOCH
3)
2+2NO
Side reaction mainly contains CO and methyl nitrite and reacts and generate NO and methylcarbonate (DMC), and methyl nitrite decomposes and generates NO, methyl-formiate and methyl alcohol, CO and NO reaction generation N
2and CO
2, chemical equation is as follows:
CO+2CH
3ONO→2NO+C
3H
6O
3
4CH
3ONO→4NO+C
2H
4O
2+2CH
3OH
2CO+2NO→N
2+2CO
2
At present, in existing technique, generally first adopt methanol absorption, after methyl alcohol, DMC and DMO being separated, the technique of variable-pressure rectification double tower or extracting rectifying double tower separation of methanol and DMC obtains pure DMO product again, and namely purification DMO need come through the technique of alcohol wash tower, alcohol recovery tower and rectifying tower.
The patent US4453026A of Ube company discloses and CO and nitrous acid (first or second) ester is reacted under platinum group noble metal catalyst, by the row condensation of reaction product limit, is separated and obtains phlegma and non-condensable gas.Adding a certain amount of methyl alcohol in the process of condensation avoids oxalic acid two (first or second) ester to be mixed into non-condensable gas and Crystallization Plugging equipment.Phlegma enters elementary rectifying tower, obtains thick oxalic acid two (first or second) ester product.
In document CN101993367A, CN101993365A, CN101993369A, CN101993361A, CN101492370A and CN101381309A, the reaction product of CO and nitrous acid ester will obtain gas phase overhead product and liquid phase overhead product through gas-liquid separation, then the liquid phase distillate containing barkite is carried out separating-purifying again and obtains thick product.Scrubber tower is separated DMO with the flow process of DMO rectifying tower to adopt primary flash to add in document CN202643601, because scrubber tower low-temperature methanol is washed, causes dimethyl oxalate at crystallization inside tower.
Disclose CO and methyl nitrite contact with platinum group noble metal catalyst in document CN101462961A and react, obtain the product of DMO and methylcarbonate.Product is entered in condenser and carry out contacting with methyl alcohol and condensation, obtain non-condensable gas and phlegma, containing DMO, methylcarbonate, methyl-formiate and methyl alcohol in phlegma.Phlegma is entered distillation tower distill, tower top obtains the azeotrope of methylcarbonate and methyl alcohol, and tower reactor obtains the material containing DMO.The method flow process is complicated, and has relatively high condensation point due to dimethyl oxalate, can crystallize out, finally block condenser in condenser wall.
In a word, in prior art, coupled product all first enters down-stream again through cooling, and technical process is complicated; Dimethyl oxalate is easy crystallization in e-quipment and pipe, and for preventing occluding device and pipeline, need be incubated or accompany heat, energy consumption is high; Meanwhile, have impact on the yield of dimethyl oxalate at e-quipment and pipe intercrystalline, thus have impact on the yield of the finished product ethylene glycol.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists technical process complexity, dimethyl oxalate Crystallization Plugging e-quipment and pipe, and material consumption and the high problem of energy consumption, provide a kind of method of production ethylene glycol newly.It is simple that the method has technical process, and energy consumption is low, and dimethyl oxalate is crystallization not easily, the feature that ethylene glycol yield is high.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind of method of producing ethylene glycol, comprises the following steps:
A) gas stream containing CO and methyl nitrite enters coupler reactor, obtains the gaseous stream containing dimethyl oxalate after reaction;
B) the described gaseous stream containing dimethyl oxalate does not cool and directly enters dimethyl oxalate recovery tower, the logistics comprising methyl alcohol enters and the described logistics counter current contact containing dimethyl oxalate from dimethyl oxalate recovery tower tower top, rectifying while absorbing, tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product stream;
C) described dimethyl oxalate product stream enters hydrogenator, obtains the logistics containing ethylene glycol after reaction;
D) product ethylene glycol is obtained containing after the stream purification of ethylene glycol described in.
In technique scheme, preferably, in described dimethyl oxalate recovery tower, described comprise methyl alcohol logistics charging place and described logistics charging place containing dimethyl oxalate between for being filled with the absorption distillation section of efficient low-resistance filler, for adopting the stripping section of valve tray between described logistics charging place containing dimethyl oxalate and tower reactor.
In technique scheme, preferably, the aspect ratio of described absorption distillation section and stripping section is 0.5 ~ 5.More preferably, the aspect ratio of described absorption distillation section and stripping section is 1 ~ 2.
In technique scheme, preferably, the operational condition of coupler reactor is: temperature of reaction 50 ~ 200 DEG C, pressure 0 ~ 1.0MPa.
In technique scheme, preferably, dimethyl oxalate recovery tower tower top service temperature is 20 ~ 60 DEG C, and working pressure is 10 ~ 100kPaG; Tower reactor service temperature is 170 ~ 200 DEG C, and working pressure is 40 ~ 150kPaG; Stripping section theoretical plate number is 5 ~ 40 pieces.
In technique scheme, preferably, the operational condition of described hydrogenator is: temperature of reaction 150 ~ 350 DEG C, pressure 1 ~ 4MPa.
In technique scheme, preferably, the pipeline between coupler reactor and dimethyl oxalate recovery tower adopts low-pressure steam to accompany heat.
In technique scheme, preferably, dimethyl oxalate recovery tower tower reactor discharge pipe adopts low-pressure steam companion heat.
In technique scheme, preferably, described coupling catalyst is platinum group metal catalysts, and hydrogenation catalyst is copper system metal catalyst.
In the inventive method, the first step is CO linked reaction synthesizing dimethyl oxalate.Gas raw material containing CO and methyl nitrite enters into the reactor being filled with solid platinum group metal catalysts and gas phase catalytic reaction occurs.Coupler reactor is calandria type fixed bed reactor, and reactor adopts circulating hot water to remove heat.The residence time of vapor-phase reactant in beds is no more than at most 12 seconds, and the suitable residence time is 0.2 ~ 6 second.Before entering the reactor, usual rare gas element is as nitrogen or CO for gas reaction raw material
2dilution.Reaction can be carried out at relatively low temperature, and typical temperature is 50 ~ 200 DEG C, and preferable temperature is 60 ~ 180 DEG C.For reaction pressure, can be 0 ~ 2MPa, be preferably 0 ~ 1MPa.In gas phase initial feed, the concentration of methyl nitrite can have a greater change scope, but in order to obtain suitable speed of reaction, the concentration of methyl nitrite is minimum must not lower than the volumetric concentration of 3%, preferably 5 ~ 30% volumetric concentrations.In gas phase initial feed, the concentration of CO also can have a greater change scope, and general control is in 10 ~ 90% volumetric concentrations.
In the inventive method, second step is the separation of dimethyl oxalate.Coupler reactor outlet reaction product does not cool and directly enters in the middle part of dimethyl oxalate recovery tower, and methyl alcohol enters and linked reaction product counter current contact from tower top, and tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product.Between methanol feeding and the charging of linked reaction product, part be absorber portion, and adopt efficient low-resistance filler, absorber portion plays rectifying section effect simultaneously, is stripping section employing valve tray containing logistics charging place of dimethyl oxalate to tower reactor part.Dimethyl oxalate recovery tower overhead gas is through condensation, and non-condensable gas part goes subsequent disposal, and a liquid phase part send subsequent disposal as the extraction of crude carbinol product, and another part mixes with methanol feeding and refluxes as dimethyl oxalate recovery tower.Coupler reactor outlet enters dimethyl oxalate recovery tower pipeline and dimethyl oxalate recovery tower tower reactor discharge pipe all adopts low-pressure steam to accompany heat, prevents dimethyl oxalate crystallization in rectifying tower e-quipment and pipe.Dimethyl oxalate recovery tower stripping section theoretical plate number is 5 ~ 40 pieces.Dimethyl oxalate recovery tower tower top service temperature is 20 ~ 60 DEG C, and working pressure is 10 ~ 100kPaG; Tower reactor service temperature is 170 ~ 200 DEG C, and working pressure is 40 ~ 150kPaG.
In the inventive method, the 3rd step is dimethyl oxalate catalytic hydrogenation.After the dimethyl oxalate product stream that dimethyl oxalate recovery tower tower reactor obtains is heated, mix with hydrogen, enter in the packed-bed reactor being filled with copper system metal catalyst and carry out gas phase catalytic reaction.Reactor can use fixed bed or fluidized-bed reactor, and gas more than 5 seconds, should not be preferably 0.2 ~ 2 second in the residence time of catalyst layer.Temperature of reaction is generally 150 ~ 350 DEG C, preferably 160 ~ 240 DEG C; Reaction pressure is not less than normal pressure, preferably 1 ~ 4MPa.This one-step process primary product is out other corresponding by products that ethylene glycol and Hydrogenation of Dimethyl Oxalate generate, such as ethyl glycolate.
In the inventive method, the 4th step is the refining of ethylene glycol.The logistics containing ethylene glycol out of catalytic hydrogenation reaction device tower reactor, after heat exchange cooling, enters in condenser and is condensed into liquid.The non-condensable gas of the hydrogen being condensed out can return in hydrogenator as hydrogen source.Lime set is introduced into pre-distillation column, and in this tower, ethylene glycol and methyl alcohol and unreacted dimethyl oxalate are separated.The methanol solution being distilled out can be used as the absorption agent of second step dimethyl oxalate recovery tower.The logistics out of pre-distillation column tower reactor enters the further separating-purifying of rectifying tower, and rectifying tower ejects the light constituent come and mainly contains ethyl glycolate.And in ethyl glycolate capable of circulation time hydrogenator.Tower bottom of rectifying tower obtain namely for the purpose of product ethylene glycol.
Adopt the inventive method, the absorption of coupled product in prior art in cooling apparatus and refining two unit operations in distillation plant are focused in a dimethyl oxalate recovery tower and completes, and coupled product does not cool and directly enters dimethyl oxalate recovery tower, makes energy consumption reduce; Prevent dimethyl oxalate crystallization in cooling apparatus, improve the yield of intermediates dimethyl oxalate, thus finally improve the yield of object product ethylene glycol; Save facility investment and floor space; Meanwhile, the simplification of flow process also makes insulation accompany the expense of heat to greatly reduce.In a word, adopt the inventive method, ethylene glycol yield can reach 100%, and capable of reducing energy consumption 60%, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic diagram.
In Fig. 1, R-101 is coupler reactor, and C-101 is dimethyl oxalate recovery tower, and R-102 is hydrogenator, and D-101 is hydrogenator outlet condenser, and D-102 is DMO recovery tower return tank, and T-101 is pre-distillation column, and T-102 is rectifying tower.1 is nitrogen feed, and 2 is CO charging, and 3 is methanol feeding, 4 is methyl nitrite charging, 5 is coupler reactor charging, and 6 is coupler reactor discharging, and 7 is absorption agent methanol feeding, 8 is dimethyl oxalate recovery tower overhead gas, 9 is dimethyl oxalate recovery tower non-condensable gas, 10 dimethyl oxalate recovery tower phegmas, 11 crude carbinol products, 12 is the logistics of dimethyl oxalate recovery tower tower reactor, and 13 is H
2, 14 is hydrogenator discharging, and 15 is the non-condensable gas of hydrogen, and 16 is condenser lime set, and 17 is pre-distillation column overhead stream, and 18 is the logistics of pre-distillation column tower reactor, and 19 is rectifying tower overhead stream, and 20 is tower bottom of rectifying tower logistics (ethylene glycol product).
In Fig. 1, nitrogen feed 1, CO charging 2, methanol feeding 3, methyl nitrite charging 4 enter coupler reactor R-101 after mixing after preheating, after there is linked reaction, reaction product 6 directly enters in the middle part of dimethyl oxalate recovery tower C-101, absorption agent methyl alcohol 7 mixes with dimethyl oxalate recovery tower phegma and enters from dimethyl oxalate recovery tower top, overhead gas 8 is after the condensation of dimethyl oxalate recovery tower overhead condenser, non-condensable gas 9 enters aftertreatment, crude carbinol product 11 extraction, dimethyl oxalate 12 is from tower reactor extraction.Wherein, logistics 6 and logistics 12 pipeline accompany heat by low-pressure steam, prevent dimethyl oxalate crystallization in rectifying tower e-quipment and pipe.After the dimethyl oxalate 12 that dimethyl oxalate recovery tower tower reactor obtains is heated, mix with hydrogen 13, enter in the packed-bed reactor R-102 being filled with copper system metal catalyst and carry out gas phase catalytic reaction.The tower reactor logistics 14 containing ethylene glycol out, after heat exchange cooling, enters in condenser D-101 and is condensed into liquid 16.The non-condensable gas 15 of the hydrogen being condensed out can return (not shown in FIG.) in hydrogenator R-102 as hydrogen source.Lime set 16 is introduced into pre-distillation column T-101, and in this tower, ethylene glycol and methyl alcohol and unreacted dimethyl oxalate are separated.The methanol solution 17 being distilled out can be used as the absorption agent (not shown in FIG.) of second step dimethyl oxalate recovery tower.The logistics 18 out of pre-distillation column tower reactor enters the further separating-purifying of rectifying tower T-102, and rectifying tower ejects the light constituent 19 come and mainly contains ethyl glycolate.And in ethyl glycolate capable of circulation time hydrogenator (not shown in FIG.).Tower bottom of rectifying tower obtain namely for the purpose of product ethylene glycol 20.
Below by embodiment, the invention will be further elaborated, but these embodiments are in no case construed as limiting scope of the present invention.
Embodiment
[embodiment 1]
Nitrogen feed 1, CO charging 2, methanol feeding 3, methyl nitrite charging 4 mix after totally 30 tons/hour, coupler reactor R-101 is entered after preheating, after there is linked reaction, reaction product 6 directly enters in the middle part of dimethyl oxalate recovery tower C-101,20 tons of/hour methyl alcohol 7 mix with dimethyl oxalate recovery tower phegma and enter from dimethyl oxalate recovery tower top, overhead gas 8 is after the condensation of dimethyl oxalate recovery tower overhead condenser, non-condensable gas 9 enters aftertreatment, crude carbinol product 11 extraction, dimethyl oxalate 12 is from tower reactor extraction.
After dimethyl oxalate 12 is heated, mix with hydrogen 13, enter in the packed-bed reactor R-102 being filled with copper system metal catalyst and carry out gas phase catalytic reaction.The tower reactor logistics 14 containing ethylene glycol out, after heat exchange cooling, enters in condenser D-101 and is condensed into liquid 16.Lime set 16 is introduced into pre-distillation column T-101, and in this tower, ethylene glycol and methyl alcohol and unreacted dimethyl oxalate are separated.The logistics 18 out of pre-distillation column tower reactor enters the further separating-purifying of rectifying tower T-102, and rectifying tower ejects the light constituent 19 come and mainly contains ethyl glycolate.What tower bottom of rectifying tower obtained is product ethylene glycol 20.
Coupler reactor condition is: temperature of reaction 110 DEG C, pressure 0.23MPa.
The aspect ratio of dimethyl oxalate recovery tower absorption distillation section and stripping section is 2, and hypomere theoretical plate number is 10 pieces; Tower top service temperature is 32 DEG C, and working pressure is 40kPaG; Tower reactor service temperature is 185 DEG C, and working pressure is 85kPaG, reboiler heat duty 4.044MW.
Hydrogenator condition is: temperature of reaction 200 DEG C, pressure 2.5MPa.
Pre-distillation column reaction conditions is: theoretical plate number is 50 pieces, and tower top service temperature is 52 DEG C.
Distillation column reactor condition is: theoretical plate number is 60 pieces, and tower top service temperature is 115 DEG C.
Ethylene glycol yield is 99.6%.
Main streams is composed as follows:
| Logistics | 5 | 6 | 12 | 14 | 18 | 20 |
| Temperature, DEG C | 110 | 120 | 185 | 178 | 172 | 166 |
| Pressure, kPaG | 210 | 110 | 84 | 2400 | -55 | -65 |
| Weight forms | ||||||
| H2 | - | - | - | 36.21％ | - | - |
| N 2 | 44.30％ | 44.30％ | - | - | - | - |
| CO | 19.08％ | 8.67％ | - | - | - | - |
| NO | 5.23％ | 16.68％ | - | - | - | - |
| Methyl nitrite | 29.74％ | 6.45％ | - | - | - | - |
| Methyl-formiate | - | 0.05％ | - | - | - | - |
| Methyl alcohol | 1.65％ | 1.70％ | - | 34.88％ | - | - |
| Methylcarbonate | - | 0.57％ | 0.15％ | - | - | - |
| Methyl glycolate | - | - | - | 0.02％ | 0.07％ | - |
| Dimethyl oxalate | - | 21.58％ | 99.85％ | - | - | - |
| Ethylene glycol | - | - | - | 28.78％ | 99.93％ | 100％ |
[embodiment 2]
Nitrogen feed 1, CO charging 2, methanol feeding 3, methyl nitrite charging 4 mix after totally 30 tons/hour, coupler reactor R-101 is entered after preheating, after there is linked reaction, reaction product 6 directly enters in the middle part of dimethyl oxalate recovery tower C-101,20 tons of/hour methyl alcohol 7 mix with dimethyl oxalate recovery tower phegma and enter from dimethyl oxalate recovery tower top, overhead gas 8 is after the condensation of dimethyl oxalate recovery tower overhead condenser, non-condensable gas 9 enters aftertreatment, crude carbinol product 11 extraction, dimethyl oxalate 12 is from tower reactor extraction.
After dimethyl oxalate 12 is heated, mix with hydrogen 13, enter in the packed-bed reactor R-102 being filled with copper system metal catalyst and carry out gas phase catalytic reaction.The tower reactor logistics 14 containing ethylene glycol out, after heat exchange cooling, enters in condenser D-101 and is condensed into liquid 16.Lime set 16 is introduced into pre-distillation column T-101, and in this tower, ethylene glycol and methyl alcohol and unreacted dimethyl oxalate are separated.The logistics 18 out of pre-distillation column tower reactor enters the further separating-purifying of rectifying tower T-102, and rectifying tower ejects the light constituent 19 come and mainly contains ethyl glycolate.What tower bottom of rectifying tower obtained is product ethylene glycol 20.
Coupler reactor condition is: temperature of reaction 150 DEG C, pressure 0.1MPa.
The aspect ratio of dimethyl oxalate recovery tower absorption distillation section and stripping section is 1.5, and hypomere theoretical plate number is 20 pieces; Tower top service temperature is 32 DEG C, and working pressure is 40kPaG; Tower reactor service temperature is 185 DEG C, and working pressure is 85kPaG, reboiler heat duty 3.265MW.
Hydrogenator condition is: temperature of reaction 220 DEG C, pressure 3.5MPa.
Pre-distillation column reaction conditions is: theoretical plate number is 50 pieces, and tower top service temperature is 52 DEG C.
Distillation column reactor condition is: theoretical plate number is 60 pieces, and tower top service temperature is 115 DEG C.
Ethylene glycol yield is 99.5%.
Main streams is composed as follows:
| Logistics | 5 | 6 | 12 | 14 | 18 | 20 |
| Temperature, DEG C | 110 | 150 | 185 | 220 | 172 | 166 |
| Pressure, kPaG | 100 | 50 | 85 | 3500 | -55 | -65 |
| Weight forms | ||||||
| H 2 | - | - | - | 39.61％ | - | - |
| N 2 | 44.30％ | 44.30％ | - | - | - | - |
| CO | 19.08％ | 8.16％ | - | - | - | - |
| NO | 5.23％ | 17.32％ | - | - | - | - |
| Methyl nitrite | 29.74％ | 5.14％ | - | - | - | --- |
| Methyl-formiate | - | 0.05％ | - | - | - | - |
| Methyl alcohol | 1.65％ | 1.70％ | - | 33.36％ | - | - |
| Methylcarbonate | - | 0.88％ | 0.15％ | - | - | |
| Methyl glycolate | - | - | - | 0.01％ | 0.04％ | - |
| Dimethyl oxalate | - | 22.44％ | 99.85％ | - | - | - |
| Ethylene glycol | - | - | - | 26.92％ | 99.96％ | 100％ |
[embodiment 3]
Nitrogen feed 1, CO charging 2, methanol feeding 3, methyl nitrite charging 4 mix after totally 30 tons/hour, coupler reactor R-101 is entered after preheating, after there is linked reaction, reaction product 6 directly enters in the middle part of dimethyl oxalate recovery tower C-101,20 tons of/hour methyl alcohol 7 mix with dimethyl oxalate recovery tower phegma and enter from dimethyl oxalate recovery tower top, overhead gas 8 is after the condensation of dimethyl oxalate recovery tower overhead condenser, non-condensable gas 9 enters aftertreatment, crude carbinol product 11 extraction, dimethyl oxalate 12 is from tower reactor extraction.
After dimethyl oxalate 12 is heated, mix with hydrogen 13, enter in the packed-bed reactor R-102 being filled with copper system metal catalyst and carry out gas phase catalytic reaction.The tower reactor logistics 14 containing ethylene glycol out, after heat exchange cooling, enters in condenser D-101 and is condensed into liquid 16.Lime set 16 is introduced into pre-distillation column T-101, and in this tower, ethylene glycol and methyl alcohol and unreacted dimethyl oxalate are separated.The logistics 18 out of pre-distillation column tower reactor enters the further separating-purifying of rectifying tower T-102, and rectifying tower ejects the light constituent 19 come and mainly contains ethyl glycolate.What tower bottom of rectifying tower obtained is product ethylene glycol 20.
Coupler reactor condition is: temperature of reaction 100 DEG C, pressure 0.1MPa.
The aspect ratio of dimethyl oxalate recovery tower absorption distillation section and stripping section is 1.2, and hypomere theoretical plate number is 30 pieces; Tower top service temperature is 29 DEG C, and working pressure is 10kPaG; Tower reactor service temperature is 178 DEG C, and working pressure is 50kPaG, reboiler heat duty 4.105MW.
Hydrogenator condition is: temperature of reaction 190 DEG C, pressure 3.0MPa.
Pre-distillation column reaction conditions is: theoretical plate number is 50 pieces, and tower top service temperature is 52 DEG C.
Distillation column reactor condition is: theoretical plate number is 60 pieces, and tower top service temperature is 115 DEG C.
Ethylene glycol yield is 99.8%.
Main streams is composed as follows:
| Logistics | 5 | 6 | 12 | 14 | 18 | 20 |
| Temperature, DEG C | 110 | 100 | 178 | 190 | 172 | 166 |
| Pressure, kPaG | 100 | 20 | 50 | 3000 | -55 | -65 |
| Weight forms | ||||||
| H 2 | - | - | - | 41.52％ | - | - |
| N 2 | 44.30％ | 44.30％ | - | - | - | - |
| CO | 19.08％ | 10.82％ | - | - | - | - |
| NO | 5.23％ | 14.16％ | - | - | - | - |
| Methyl nitrite | 29.74％ | 11.57％ | - | - | - | - |
| Methyl-formiate | - | 0.01％ | - | - | - | - |
| Methyl alcohol | 1.65％ | 1.65％ | - | 32.50％ | - | - |
| Methylcarbonate | - | 0.22％ | 0.14％ | - | - | |
| Methyl glycolate | - | - | - | 0.06％ | 0.21％ | - |
| Dimethyl oxalate | - | 17.26％ | 99.86％ | - | - | - |
| Ethylene glycol | - | - | - | 25.87％ | 99.79％ | 100％ |
Claims (10)
1. produce a method for ethylene glycol, comprise the following steps:
A) gas stream containing CO and methyl nitrite enters coupler reactor, obtains the gaseous stream containing dimethyl oxalate after reaction;
B) the described gaseous stream containing dimethyl oxalate does not cool and directly enters dimethyl oxalate recovery tower, the logistics comprising methyl alcohol enters and the described logistics counter current contact containing dimethyl oxalate from dimethyl oxalate recovery tower tower top, rectifying while absorbing, tower top obtains crude carbinol and non-condensable gas, and tower reactor obtains dimethyl oxalate product stream;
C) described dimethyl oxalate product stream enters hydrogenator, obtains the logistics containing ethylene glycol after reaction;
D) product ethylene glycol is obtained containing after the stream purification of ethylene glycol described in.
2. produce the method for ethylene glycol according to claim 1, it is characterized in that in described dimethyl oxalate recovery tower, described comprise methyl alcohol logistics charging place and described logistics charging place containing dimethyl oxalate between for load Packed absorption distillation section, described containing between logistics charging place of dimethyl oxalate and tower reactor is the stripping section adopting valve tray.
3. produce the method for ethylene glycol according to claim 2, it is characterized in that the aspect ratio of described absorption distillation section and stripping section is 0.5 ~ 5.
4. produce the method for ethylene glycol according to claim 3, it is characterized in that the aspect ratio of described absorption distillation section and stripping section is 1 ~ 2.
5. produce the method for ethylene glycol according to claim 1, it is characterized in that the operational condition of described coupler reactor is: temperature of reaction 50 ~ 200 DEG C, pressure 0 ~ 1.0MPa.
6. produce the method for ethylene glycol according to claim 1, it is characterized in that dimethyl oxalate recovery tower tower top service temperature is 20 ~ 60 DEG C, working pressure is 10 ~ 100kPaG; Tower reactor service temperature is 170 ~ 200 DEG C, and working pressure is 40 ~ 150kPaG; Stripping section theoretical plate number is 5 ~ 40 pieces.
7. produce the method for ethylene glycol according to claim 1, it is characterized in that the operational condition of described hydrogenator is: temperature of reaction 150 ~ 350 DEG C, pressure 1 ~ 4MPa.
8. produce the method for ethylene glycol according to claim 1, it is characterized in that the pipeline between coupler reactor and dimethyl oxalate recovery tower adopts low-pressure steam to accompany heat.
9. produce the method for ethylene glycol according to claim 1, it is characterized in that dimethyl oxalate recovery tower tower reactor discharge pipe adopts low-pressure steam companion heat.
10. produce the method for ethylene glycol according to claim 1, it is characterized in that described coupling catalyst is platinum group metal catalysts, hydrogenation catalyst is copper system metal catalyst.
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| CN107954830A (en) * | 2016-10-17 | 2018-04-24 | 上海浦景化工技术股份有限公司 | A kind of method of product separating energy consumption in reduction preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN109096049A (en) * | 2018-07-03 | 2018-12-28 | 沈阳化工大学 | A kind of method that esterification eliminates dimethyl ester mesoxalic acid and obtains polyester grade ethylene glycol |
| CN111269084A (en) * | 2018-12-04 | 2020-06-12 | 上海浦景化工技术股份有限公司 | Method for removing methyl formate and/or dimethyl carbonate in methanol |
| CN112479814A (en) * | 2019-09-12 | 2021-03-12 | 南京延长反应技术研究院有限公司 | Reaction system and process for strengthening hydrogenation of dimethyl oxalate in coal-to-ethylene glycol |
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