CN102731300B - Industrialization method for producing dimethyl oxalate by continuous cycle esterification and coupling carbonylation - Google Patents
Industrialization method for producing dimethyl oxalate by continuous cycle esterification and coupling carbonylation Download PDFInfo
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- CN102731300B CN102731300B CN201110088470.4A CN201110088470A CN102731300B CN 102731300 B CN102731300 B CN 102731300B CN 201110088470 A CN201110088470 A CN 201110088470A CN 102731300 B CN102731300 B CN 102731300B
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 168
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 230000032050 esterification Effects 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 24
- 230000006315 carbonylation Effects 0.000 title claims abstract description 23
- 238000005859 coupling reaction Methods 0.000 title abstract description 4
- 230000008878 coupling Effects 0.000 title abstract 2
- 238000010168 coupling process Methods 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 213
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 65
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 62
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 60
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000746 purification Methods 0.000 claims abstract description 7
- 230000002000 scavenging effect Effects 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000012856 packing Methods 0.000 claims description 16
- 239000002516 radical scavenger Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 36
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 238000000066 reactive distillation Methods 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 230000009719 regenerative response Effects 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 8
- 238000003672 processing method Methods 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- -1 nitrous acid ester Chemical class 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000007115 recruitment Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241000611009 Nematalosa come Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003842 industrial chemical process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to an industrialization method for producing dimethyl oxalate by continuous cycle esterification and coupling carbonylation. The method comprises steps of, (1), esterification reaction, wherein methanol, O2 and nitrogen oxides enter a reaction zone of an esterification reaction tower in a concurrent flow and a reaction is carried out to generate methyl nitrite; liquid flow generated after the reaction flows out from a bottom outlet of the esterification reaction tower and cycles back to the reaction zone of the esterification reaction tower; a gas flow generated after the reaction flows out from the bottom outlet of the esterification reaction tower, and methyl nitrite is obtained by purification and dry; the esterification reaction tower is a packed column; (2), CO carbonyl synthesis reactor, wherein CO and methyl nitrite obtained in step (1) perform coupling reaction in a carbonyl synthesis reactor and generate dimethyl oxalate, and regenerate NO; and NO returns to the esterification reaction tower in step (1). By employing the method, a small factory investment, a stable device operation and a high selectivity of generating methyl nitrite by oxidation reaction and esterification reaction are guaranteed.
Description
Technical field
The present invention relates to a kind of continuous circulation esterification and oxo process dimethyl oxalate technique, specifically, relating to a kind of is that material oxidation carbonylation is coupled the industrial chemical process producing dimethyl oxalate by CO.
Background technology
It is a kind of known chemical reaction that CO oxidative carbonylation is coupled oxalic dimethyl ester.By introducing methyl nitrite as strong oxidizer, at Pd/Al
2o
3under catalyzer, CO at suitable temperature and reaction pressure condition with methyl nitrite generation carbonylation coupled reaction oxalic dimethyl ester, and regenerate NO.Dimethyl oxalate be not only for be hydrolyzed prepare oxalic acid most competition raw material sources, prior and maximum purposes be for hydrogenating materials to prepare ethylene glycol, there is extremely important business development using value.
Some other processing method embodiments that CO oxidative carbonylation is coupled oxalic dimethyl ester can find in published Chinese patent CN 101190884A, CN 101475472A, CN 101462961A in recent years, and these documents are enumerated in this as reference.
The formation reaction of methyl nitrite is defined as regenerative response in this technical process, generally by arranging a reactive distillation column on stream to realize.Regenerative response is easy to carry out, and does not need catalyzer, and reaction conditions is gentle.The preparation of methyl nitrite (MN, Methyl Nitrite), main reaction is:
Side reaction: CH
3oH+N
2o
4→ CH
3oNO+HNO
3
3N
2O
3+H
2O(g)→2HNO
3+4NO
In regeneration reaction system, main reactant is methyl alcohol, NO and O
2.Owing to there is NO and O in reaction system
2, cause nitrogen oxide in this reaction system various informative, and be in unstable change procedure always, comprise NO, NO
2, N
2o
3, N
3o
4, the effective oxide wherein participating in reaction generation methyl nitrite is N
2o
3, remaining oxide compound is at generation N
2o
3while also can there is the side reaction generating the materials such as nitric acid.In esterification reaction tower, achieve the oxidizing reaction of NO before this, then generate MN with methyl alcohol generation esterification.For improving the selectivity of main reaction methyl nitrite, suppress the generation of side reaction nitric acid, usually one of measure taked mainly exports the charge proportion of the NO looped back by the suitable oxygen of allotment and carbonyl synthesis reactor, impel the nitrogen oxide in esterification reaction tower system towards being conducive to generating N
2o
3direction carry out.As NO and the O described in patent CN 101190884A
2proportional range be 0.01 ~ 0.1: 1, inherently namely improve N
2o
3generation, and then add the selectivity of MN.Oxidizing reaction and the esterification generating methyl nitrite, in order to improve the selectivity of MN, are carried out by patent CN101096340A respectively in two reactors, and a part generates NO
2oxidizing reaction carry out in pre-reactor, enter in esterification reaction tower the esterification regeneration completing and generate MN after realizing NO partial oxidation reaction again, and realize being separated of MN and nitric acid and water by the mode of reactive distillation.
Reactive distillation column generally selects tray column or packing tower all can realize, and as adopted sieve-tray tower, valve tray column in some example, and the application of packing tower is also a kind of mode comparatively widely.
Because nitrogen oxide conversion reaction is a volume-diminished reaction process, and reactions all in esterification system is strong exothermal reaction, is conducive to reaction carries out from thermodynamics analysis reduction temperature increase pressure.
Existing technology generally takes two kinds of solutions to remove to a large amount of reaction heat that esterification regenerative response produces:
A solution on column plate, arranges interchanger remove reaction heat by recirculated cooling water, this mode can realize temperature distribution on all column plates of whole reactive distillation column preferably and keep relatively consistent, improves MN esterification selectivity by regulating suitable temperature of reaction on column plate.But the weak point of this technique is that the corresponding design and manufacture cost of reactive distillation column can significantly increase, the heat-exchange equipment simultaneously increased on column plate can increase the resistance of whole circulating reaction system, and then causes the power consumption of compressor significantly to rise.
Another kind of solution is outside reactive distillation column, arrange one group or multiple external heat exchanger, the reaction solution on column plate is returned higher level's column plate by pump after external heat exchanger cooling and enters reaction zone again, and doing the benefit brought like this is that device fabrication cost reduces.Obviously, the back-mixing of reaction solution can reduce the efficiency of reactive distillation greatly, is unfavorable for the carrying out of regenerative response.
Existing methyl nitrite production technology is generally realized by the mode of reactive distillation, and this operates for the reactive distillation column that is connected in same circulation loop with oxonation device, can bring larger difficulty.Because a large amount of recycle gas passes through rectifying tower, especially when the load of production plant is in adjustment state, be in normal work operating mode needs constantly adjust vapour/liquor ratio for meeting rectifying tower, this adjustment often brings potential work accident as there is " dry plate " or " flooding " etc.
The obvious weak point that also has of this kind of technique is, a large amount of recycle gas is when leaving reactive distillation column, even if installed mist tripping device at tower top, still can carry other objectionable impuritiess produced in the water of state of saturation, micro-nitric acid and some reaction process secretly, it is fatal that these materials enter carbonyl synthesis reactor to synthetic catalyst.Implementing complete purifying treatment, usually carrying out subcooling circulation gas by arranging refrigerating apparatus, not only significantly increase plant investment and process cost, also can cause direct impact to the change of carbongl group synthesis reaction processing condition.
Therefore, need to produce a kind of continuous circulation esterification and oxo process dimethyl oxalate technique, this technique not only will realize the object stablized, oxidation and esterification generate MN efficiently under any operating mode, but also to guarantee that entering the water in the recycle gas of oxonation device, micro-nitric acid and other objectionable impuritiess is eliminated substantially, with the long-period stable operation of the maximum utilization and catalyzer that realize NO and CO.
Summary of the invention
The object of the present invention is to provide the industrial method of a kind of continuous circulation esterification and oxo process dimethyl oxalate technique, with alap factory construction cost and running cost, realize stable operation and be oxidized and esterification highly selective, and the objectionable impurities entered in the recycle gas of carbonyl synthesis reactor is reached and meets its reaction requirement, the prolongation oxo catalyst working time of maximum possible.
For achieving the above object, the present invention adopts following technical scheme:
Continuous circulation esterification and carbonylation are coupled the industrial method producing dimethyl oxalate, comprise the steps:
1) esterification: make methyl alcohol, O
2with nitrogen oxide and the reaction zone flow to into esterification reaction tower, and carry out reaction and generate methyl nitrite; The liquid stream produced after reaction flows out from esterification reaction tower outlet at bottom and circulates and returns to the reaction zone of esterification reaction tower; The gas stream produced after reaction flows out from esterification reaction tower lower part outlet, and after purification and drying, obtains the mixed gas containing reaction product methyl nitrite successively; Described esterification reaction tower is packing tower;
2) CO carbongl group synthesis reaction: make CO and step 1) in the methyl nitrite that obtains in carbonyl synthesis reactor, there is carbonylation linked reaction oxalic dimethyl ester, and regenerate NO; NO returns step 1) in esterification reaction tower.
Step 1) in, the liquid stream gone out from esterification tower bottom flow is mainly unreacted methyl alcohol, containing esterification reaction product methyl nitrite in gas stream.
Described nitrogen oxide is NO, NO
2, N
2o
3and N
3o
4in one or more arbitrary combination.
Preferably, the charging of esterification reaction tower is selected from one of following manner:
Methyl alcohol, O
2flow to into reaction zone with nitrogen oxide from esterification tower top sparger;
O
2from charging between the packing section on esterification reaction tower top, and flow to into reaction zone with the methyl alcohol entered by tower distributor and nitrogen oxide.
Further, from liquid stream out at the bottom of esterification reaction tower tower after water cooler cooling recirculation return to the reaction zone of esterification reaction tower.By liquid stream in the external circulation of esterification reaction tower and heat exchange, a large amount of Heat of Formations esterification produced are very convenient and be easy to remove.
Preferably, the temperature of described esterification is 20 DEG C ~ 95 DEG C, is preferably 30 DEG C ~ 90 DEG C.The selectivity that the selectivity of NO oxidation in this temperature range and MN regenerate is all that optimum, the too high or too low regeneration of temperature to the oxidation of NO or MN all disadvantageous chemical reaction can occur, and final result shows that in system, the magnitude of recruitment of NO adds.
In addition, also be very crucial to the control of esterification reaction pressure, because esterification reaction pressure not only affects the oxidation of NO and the regenerative response of MN, but also can have influence on the process of oxonation oxalic dimethyl ester, the economical operation of device and construction investment also tool are had a great impact.Preferably, described esterification reaction pressure is 0.005-1.0MPa (G), is preferably 0.1-0.7MPa (G).
In above-mentioned continuous processing operational process provided by the present invention, needing the successive volume ratio supplying CO and oxygen to be 8 ~ 2: 1 (v/v), the NO of esterification reaction tower import and the volume ratio of oxygen is 3 ~ 12: 1 (v/v); The methyl alcohol of esterification reaction tower import and the mol ratio of oxygen are 15 ~ 5: 1.The formation of CO raw material can be formed as the method for the hydrocarbon conversion by gasification known in the art or other, and oxygen adopts the way of low temperature separation process to realize usually, and NH is passed through in the source of NO
3oxidizing process or the relevant nitrogenous inorganic salt of utilization transform and obtain.
Under normal circumstances, for the regenerative response of the oxidation and MN that meet NO normally carries out, recycle gas controls at 1 ~ 200 second in the residence time of esterification reaction tower, and the minimizing of the residence time and prolongation are all to reacting unfavorable.
The exit gas logistics of esterification reaction tower is mainly product nitrous acid ester, directly enters scavenging tower lower entrances, and from the scavenging agent counter current contact purifying tower top, is purified the gas stream of esterification outlet by scavenging agent.The preferred scavenging agent of the present invention is water.The service temperature of scavenging tower can at 10 DEG C ~ 60 DEG C, preferably 25 ~ 60 DEG C.Certainly, lower service temperature should be adopted as far as possible for improving decontamination effect improving.Described scavenging tower is tray column or packing tower.
The methyl nitrite gas dew point exported to make scavenging tower reaches the requirement meeting oxonation, and the present invention is provided with one group of moisture eliminator in operational path, adopts in parallel or series system connection between each moisture eliminator.The siccative used in moisture eliminator generally selects aluminum oxide or molecular sieve.In factory's operational process, moisture eliminator is on-line operation always, and by switching and regenerating, ensures that another moisture eliminator is in stand-by state at any time.The dew-point temperature of dried gas material can be controlled in-60 DEG C to-5 DEG C.
Entered in carbonyl synthesis reactor by moisture eliminator reaction mass methyl nitrite out and carbonylation linked reaction oxalic dimethyl ester occurs with CO, and regenerate NO.Preferably, the entrance temperature of reaction controlling carbonyl synthesis reactor is 80 DEG C ~ 165 DEG C.Pd/Al is loaded in carbonyl synthesis reactor
2o
3catalyzer, temperature of reaction controls at 110 DEG C ~ 195 DEG C, and reaction pressure controls at 0.1 ~ 1.0MPa.
Carbonylation linked reaction generates product dimethyl oxalate and a small amount of by product, the outlet streams of carbonyl synthesis reactor isolates the thick product of dimethyl oxalate after thick reactor product cooler cooling, noncondensable gas enters Methanol Wash Column and isolate NO after methanol wash, and circulation returns esterification reaction tower entrance.
Further, be mainly methyl alcohol through the isolated liquid stream of Methanol Wash Column, and containing a small amount of dimethyl oxalate, this liquid stream enters dimethyl oxalate knockout tower, isolates methyl alcohol and dimethyl oxalate.
According to the preferred method of the present invention, carbonyl synthesis reactor reacts that the heat that produces reclaimed by the mode of byproduct steam, the usual pressure range of the steam produced is at 0.4-1.3MPa (G), and this burst of low-pressure steam can be used for the heating of dimethyl oxalate, product thermal treatment, rectifying and boiler supply water deaerating, barkite pipeline companion heat etc.
The main difference part of the present invention and prior art is, in fact esterification reaction tower of the present invention is equivalent to a plug flow reactor, and these are completely different from reactive distillation used in the prior art.The regeneration esterification of methyl nitrite (MN) is carried out by the present invention in packing tower, essentially provides a best esterification solution.Contriver thinks, realize optimum MN regenerative process, suitable process operation parameter, technical process have same importance with the selection of equipment.In the present invention, esterification reaction tower is not a reactor with refinery distillation, and is completely a plug flow reactor, all reactant flow from reaction tower top or top and flow to into reaction tower reaction, fresh methyl alcohol, fresh O
2and export from carbonyl synthesis reactor the NO that loops back and flow to into esterification reaction tower, in esterification reaction tower, realize the oxidation of NO and the regenerative response of MN.Esterification reaction tower in the present invention selects packing tower, and the Main Function of filler increases gas/liquid phase interface contact area, also serves the effect being conducive to gas and vapor permeation and dispersion simultaneously.
Obviously, esterification reaction tower outlet or bottom block column plate liquid stream major part are looped back top of tower and enters reaction zone again, because this liquid phase stream major part is unreacted methanol solution, this flow process is equivalent to add liquid dispersion process, break traditional rectifying theory, also serve vital effect in the present invention.A large amount of unreacted methanol solution circulation, owing to significantly adding filler liquid holdup, excessive methanol serves promoter action for esterification on the one hand; On the other hand, the methyl alcohol of a large amount of circulation is also conducive to the absorption of esterification Heat of Formation and takes out of, serve keying action for control temperature of reaction, and by esterification reaction tower extracorporeal circulation and heat exchange, a large amount of Heat of Formations that esterification produces can be very convenient and be easy to remove.
Further in particular, the methanol loop system that esterification reaction tower of the present invention provides, for stabilizing esterification reaction temperature with to provide excessive methyl alcohol to carry out esterification be very favorable.
The more important thing is, adopt processing method of the present invention, plant operator is in actual moving process, esterification operation can be carried out easily, especially when the load of production plant is in adjustment state, even if recycle gas flow is large in this technological process, also need not be in normal work operating mode for meeting rectifying tower and constantly adjusts vapour/liquor ratio as operation rectifying tower, thoroughly avoiding potential work accident as there is " dry plate " or " flooding " etc.
Processing method of the present invention is adopted to also have an obvious benefit to be, by purification, the drying of scavenging tower and moisture eliminator, substantially eliminate esterification reaction tower and eject other objectionable impuritiess produced in the water of gas entrained with, micro-nitric acid and some reaction process, and these materials enter carbonyl synthesis reactor to synthetic catalyst is fatal.Thus can make carbongl group synthesis reaction catalyzer can long-period stable operation.
The present invention further discloses and a kind ofly realizes the device that above-mentioned continuous circulation esterification and carbonylation are coupled the industrial method producing dimethyl oxalate, comprising: esterification reaction tower, methanol loop pump, scavenging tower, moisture eliminator, carbonyl synthesis reactor, thick reactor product cooler and Methanol Wash Column; Wherein: the bottoms liquid stream outlet of esterification reaction tower is connected through pipeline with the top entry of esterification reaction tower by methanol loop pump, and the lower gas stream outlet of esterification reaction tower is connected through pipeline with the bottom inlet of scavenging tower; The tower top outlet of scavenging tower is connected through pipeline with the entrance of moisture eliminator; The outlet of moisture eliminator is connected through pipeline with the entrance of carbonyl synthesis reactor; The outlet of carbonyl synthesis reactor is connected through pipeline with the entrance of thick reactor product cooler; The outlet of thick reactor product cooler is connected through pipeline with the lower entrances of Methanol Wash Column; The top exit of Methanol Wash Column is connected through pipeline with the top entry of esterification reaction tower; Described esterification reaction tower is packing tower.
Further, the top exit of Methanol Wash Column is connected through pipeline with the top entry of esterification reaction tower by recycle compressor.
Further, said apparatus also comprises the methyl alcohol water cooler be located between methanol loop pump and the top entry of esterification reaction tower.For cooling the external recycle stream of esterification reaction tower, thus a large amount of Heat of Formations esterification produced are very convenient and be easy to remove.
Further, said apparatus also comprises dimethyl oxalate knockout tower, and the entrance of dimethyl oxalate knockout tower is connected through pipeline with the outlet at bottom of Methanol Wash Column.For separating of the methanol solution containing a small amount of dimethyl oxalate flowed out from Methanol Wash Column.
The present invention still further provides a kind of industrial method producing dimethyl oxalate, comprises the steps: to make methyl alcohol, O
2with nitrogen oxide and the reaction zone flow to into esterification reaction tower, and carry out reaction and generate methyl nitrite; The liquid stream produced after reaction flows out from esterification reaction tower outlet at bottom and circulates and returns to the reaction zone of esterification reaction tower; The gas stream produced after reaction flows out from esterification reaction tower lower part outlet, and after purification and drying, obtains methyl nitrite successively; Described esterification reaction tower is packing tower.
The liquid stream gone out from esterification tower bottom flow is mainly unreacted methyl alcohol, and gas stream is mainly product methyl nitrite.
Described nitrogen oxide is NO, NO
2, N
2o
3and N
3o
4in one or more arbitrary combination.
Preferably, the charging of esterification reaction tower is selected from one of following manner:
Methyl alcohol, O
2flow to into reaction zone with nitrogen oxide from esterification tower top sparger;
O
2from charging between the packing section on esterification reaction tower top, and flow to into reaction zone with the methyl alcohol entered by tower distributor and nitrogen oxide.
Further, from liquid stream out at the bottom of esterification reaction tower tower after water cooler cooling recirculation return to the reaction zone of answering esterification reaction tower.By liquid stream in the external circulation of esterification reaction tower and heat exchange, a large amount of Heat of Formations esterification produced are very convenient and be easy to remove.
Preferably, the temperature of described esterification is 20 DEG C ~ 95 DEG C, is preferably 30 DEG C ~ 90 DEG C.The selectivity that the selectivity of NO oxidation in this temperature range and MN regenerate is all that optimum, the too high or too low regeneration of temperature to the oxidation of NO or MN all disadvantageous chemical reaction can occur, and final result shows that in system, the magnitude of recruitment of NO adds.
In addition, also be very crucial to the control of esterification reaction pressure, because esterification reaction pressure not only affects the oxidation of NO and the regenerative response of MN, but also can have influence on the process of oxonation oxalic dimethyl ester, the economical operation of device and construction investment also tool are had a great impact.Preferably, described esterification reaction pressure is 0.005-1.0MPa (G), is preferably 0.1-0.7MPa (G).
In above-mentioned continuous processing operational process provided by the present invention, needing the successive volume ratio supplying CO and oxygen to be 8 ~ 2: 1 (v/v), the NO of esterification reaction tower import and the volume ratio of oxygen is 3 ~ 12: 1 (v/v); The methyl alcohol of esterification reaction tower import and the mol ratio of oxygen are 15 ~ 5: 1.The formation of CO raw material can be formed as the method for the hydrocarbon conversion by gasification known in the art or other, and oxygen adopts the way of low temperature separation process to realize usually, and NH is passed through in the source of NO
3oxidizing process or the relevant nitrogenous inorganic salt of utilization transform and obtain.
Under normal circumstances, for the regenerative response of the oxidation and MN that meet NO normally carries out, recycle gas controls at 1 ~ 200 second in the residence time of esterification reaction tower, and the minimizing of the residence time and prolongation are all to reacting unfavorable.
The exit gas logistics of esterification reaction tower is mainly product nitrous acid ester, directly enters scavenging tower lower entrances, and from the scavenging agent counter current contact purifying tower top, is purified the gas stream of esterification outlet by scavenging agent.The preferred scavenging agent of the present invention is water.The service temperature of scavenging tower can at 10 DEG C ~ 60 DEG C, preferably 25 ~ 60 DEG C.Certainly, lower service temperature should be adopted as far as possible for improving decontamination effect improving.Described scavenging tower is tray column or packing tower.
The methyl nitrite gas dew point exported to make scavenging tower reaches the requirement meeting oxonation, and the present invention is provided with one group of moisture eliminator in operational path, adopts in parallel or be connected in series mode between each moisture eliminator.The siccative used in moisture eliminator generally selects aluminum oxide or molecular sieve.In factory's operational process, moisture eliminator is on-line operation always, and by switching and regenerating, ensures that another moisture eliminator is in stand-by state at any time.The dew-point temperature of dried gas material can be controlled in-60 DEG C to-5 DEG C.
Aforesaid method provided by the present invention, plant investment can not only be realized minimize with implement device stable operation and to be oxidized and the highly selective of esterification generates the object of methyl nitrite, and can also guarantee that entering the water in the recycle gas of oxonation device, micro-nitric acid and other objectionable impuritiess is eliminated substantially, guarantee to realize the maximum utilization of NO and CO and the long-period stable operation of carbongl group synthesis reaction catalyzer.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
As shown in Figure 1, the device for realizing processing method of the present invention at least comprises: the external methyl alcohol water cooler 9 of esterification reaction tower 1, methanol loop pump 2, esterification reaction tower, scavenging tower 3, moisture eliminator 4, carbonyl synthesis reactor 5, thick reactor product cooler 6, Methanol Wash Column 7, recycle compressor 10 and DMO (dimethyl oxalate) knockout tower 8.Should understand, in specific implementation process, the off-set facility such as other equipment that may use such as Raw material pail, vacuum meter, variable valve, temperature measuring set, pressure transmitter, storage tank all implement all fours with conventional chemical engineering, and these are emphasis place of the present invention not.In addition, various equipment mentioned in the present invention all can increase and decrease equipment number of units on demand, or also can increase the facilities such as such as thick product separation tank, preheater.
As shown in Figure 1, liquid methanol is by pipeline 12, O
2by pipeline 11 and the circulation gas NO looped back from carbonyl synthesis reactor 5 together and flow to into esterification reaction tower 1, liquid methanol and gas stream are distributed on the tower top filler of esterification reaction tower 1 by the sparger being arranged on tower top.Liquid exit at the bottom of tower delivers to methanol loop pump 2 through pipeline, then delivers to external methyl alcohol water cooler 9 by recycle pump 2 through pipeline, and the top that cooled methanol solution returns esterification reaction tower 1 enters reaction zone reaction again.Therefore, the circular flow by controlling methyl alcohol just can be good at controlling temperature range required in esterification reaction tower.Equally, can be good at by the size of flow director control inlet stream the ratio regulating NO and oxygen, CO and oxygen.
Liquid level at the bottom of the tower of suitable esterification reaction tower 1 is controlled by fluid level controller, in esterification reaction tower 1, reacted gaseous stream leaves esterification reaction tower 1 and directly enters bottom or the bottom inlet of scavenging tower 3, component in this gaseous phase materials mainly esterification generate MN, unreacted CO, NO, methyl alcohol, water and by-product trace nitric acid etc., after absorbing with the abundant counter current contact of detergent water from pipeline 13 in scavenging tower, gaseous stream leaves scavenging tower 3 by scavenging tower 3 top.Scavenging tower 3 top can be returned to, less part removal system by a tower bottom outlet 14 scavenging agent part out for scavenging tower 3.
Directly pass into the entrance of a moisture eliminator 4 from scavenging tower 3 gaseous stream out, control dried recycle gas dew point within the scope of-40 DEG C to-5 DEG C.Dried gas is mixed with the fresh CO supplemented by pipeline 15 and is heated to after oxonation device 5 temperature in through preheater, enters in oxonation device 5, and at Pd/Al
2o
3catalyzer is deposited and is carried out carbonylation reaction in case, oxalic dimethyl ester, and regenerates NO.The temperature of oxonation device 5, by regulating the pressure of drum provided thereon to control, controls oxonation temperature between 110 DEG C to 195 DEG C usually.
The outlet of oxonation device 5 is connected with the entrance of thick reactor product cooler 6, and this water cooler generally adopts tempered water that the dimethyl oxalate that oxonation generates is cooled to dew-point temperature, and liquid phase dimethyl oxalate isolates the thick product of dimethyl oxalate by separating tank.By in thick reactor product cooler 6 out containing a large amount of circulation gas of dimethyl oxalate, connect through pipeline and send into Methanol Wash Column 7, sloughed completely by dimethyl oxalate remaining in circulation gas in this tower, gas NO out returns esterification reaction tower 1 by recycle compressor 10 by the top of Methanol Wash Column 7.The methyl alcohol that Methanol Wash Column 7 methyl alcohol used can use DMO knockout tower 8 to reclaim.In factory's implementation process, the pipeline of the connection top exit of Methanol Wash Column 7 and the top entry of esterification reaction tower 1 arranges a pressure regulating device usually, by controlling the pressure ensureing oxonation and the whole recycle system of flow discharge unit inertia off-gas, meet carbonylation and esterification reaction pressure demand.
Methanol Wash Column 7 outlet at bottom liquid is out the methanol solution containing dimethyl oxalate, is sent to DMO knockout tower 8 carries out methyl alcohol and DMO product separation by pipeline, and the methyl alcohol produced after being separated is flowed out by tower top pipeline 17, and DMO is flowed out by tower bottom pipeline 18.This tower can operate at ambient pressure, and bottom temperature controls between 65-85 DEG C.
Above-mentioned technological process provided by the present invention is illustrated with the equipment such as carbonyl synthesis reactor, esterification reaction tower, but is appreciated that in appropriate circumstances, and the number of some or all these equipment all can increase.
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1
Processing method as above is adopted to produce dimethyl oxalate.
(1) raw material liq methyl alcohol 2000kg/h is pressurized to by pump the top sparger that 0.7MPa (G) is sent to esterification reaction tower 1,200Nm
3/ h 0.5 ~ 1MPa (G) oxygen is sent to the top sparger of esterification reaction tower 1 by pipeline 11, and the circulation gas of coming with recycle compressor 10 force feed mixes and flows to and reacts into filler reaction zone.The oxidation of NO and esterification all occur in whole space reactor.By opening the methanol loop pump 2 of esterification reaction tower 1 outlet at bottom, 20t/h methanol solution being delivered to after external methyl alcohol water cooler 9 cools and returning esterification reaction tower 1 top-heavy new distributing.Esterification control temperature 85 DEG C, the selectivity that reaction pressure 0.65MPa (G), NO are converted into MN can reach 96%.
(2) esterification reaction tower 1 exports reactant gases (circulation gas) total amount is 22000Nm
3/ h, gaseous fraction mainly esterification generate MN, unreacted CO, NO, methyl alcohol, water and by-product trace nitric acid etc., be sent to bottom scavenging tower 3 by pipeline, with scavenging agent water counter current contact, the recycle gas after purification leaves from tower top and enters moisture eliminator 4.A tower bottom outlet scavenging agent part for scavenging tower 3 can return to scavenging tower 3 top, less part removal system.The working pressure 0.55MPa (G) of scavenging tower 3, service temperature 25 DEG C.
(3) recycle gas leaving scavenging tower 3 enters moisture eliminator 4, is filled with activated alumina ball or molecular sieve in moisture eliminator 4, and after adsorbent moisture, circulation gas dew point controls at-40 DEG C.Come into operation in process at moisture eliminator, by the dew-point temperature variation tendency of analysis cycle gas, moisture eliminator will be switched in time, and by regeneration to guarantee that moisture eliminator is in online stand-by state.
(4) the fresh CO raw material gas flow supplemented is 1000Nm
3/ h mixes with the recycle gas leaving moisture eliminator 4, enters carbonyl synthesis reactor 5, at Pd/Al through preheater heat exchange to 90 DEG C
2o
3catalyzer is deposited and is carried out building-up reactions in case.Temperature of reaction controls at 170 DEG C by regulating drum pressure, reaction pressure controls at 0.55MPa (G), reaction product is dimethyl oxalate, methylcarbonate, dme, methyl-formiate etc., all the other trace and even traces, the selectivity of its dimethyl oxalate in preparation is 99%, the transformation efficiency 80% of methyl nitrite.Exit gas component also has unreacted CO, the NO of methyl nitrite, reaction regeneration and rare gas element N
2.
(5) after carbonyl synthesis reactor 5 exit gas leaves reactor, through thick reactor product cooler 6, the dimethyl oxalate that reaction generates is cooled to dew-point temperature, separate as thick product after the cooling of major part dimethyl oxalate, in recycle gas, uncooled dimethyl oxalate is after Methanol Wash Column 7 washs, and is sent to recycle compressor 10 entrance.One flow control valve is set at compressor 10 entrance and puts by speeding the pressure-stabilisation that small portion rare gas element guarantees whole reaction system.Recycle gas after methanol wash column compresses after pressure-raising to 0.68MPa (G) through recycle compressor 10, enters esterification reaction tower 1 top entry by pipeline.
(6) methanol solution containing dimethyl oxalate washed, mixes with the dimethyl oxalate separated and is together sent to DMO knockout tower 8, and this tower maintains micro-pressure operation, and tower reactor service temperature 160 DEG C, tower top temperature is 70 DEG C.
Producing dimethyl oxalate according to this processing method is 2500kg/h, dimethyl oxalate purity 99.5%, CO unit consumption≤500Nm
3/ t.DMO.
Embodiment 2
The processing method repeated described in embodiment 1 produces dimethyl oxalate.But the inlet amount changing esterification reaction tower methyl alcohol is 6000Kg/h, oxygen feeding amount 800Nm
3/ h, removes esterification heat by external methyl alcohol water cooler 9, and control esterification reaction temperature 30 DEG C, the selectivity that reaction pressure 0.1MPa (G), NO are converted into MN can reach 99%.
Esterification reaction tower exit gas is after super-dry, and dew point controls-20 DEG C and leaves moisture eliminator, is 2900Nm with the fresh CO gas flow supplemented
3/ h mixing is preheating to 150 DEG C through carbonyl synthesis reactor 5 inlet preheater and enters reactor, at Pd/Al
2o
3catalyzer is deposited and is carried out building-up reactions in case.Temperature of reaction controls at 190 DEG C by regulating drum pressure, reaction pressure controls at 0.75MPa (G), reaction product is dimethyl oxalate, methylcarbonate, dme, methyl-formiate etc., all the other trace and even traces, the selectivity of its dimethyl oxalate in preparation is 99.5%, the transformation efficiency 90% of methyl nitrite.Exit gas component also has unreacted CO, the NO of methyl nitrite, reaction regeneration and rare gas element N2.
Producing dimethyl oxalate according to this processing method is 7500kg/h, dimethyl oxalate purity 99.5%, CO unit consumption≤480Nm
3/ t.DMO.
Claims (16)
1. continuous circulation esterification and carbonylation are coupled the industrial method producing dimethyl oxalate, comprise the steps:
1) esterification: make methyl alcohol, O
2with nitrogen oxide and the reaction zone flow to into esterification reaction tower, and carry out reaction and generate methyl nitrite; The liquid stream produced after reaction cools through water cooler the reaction zone that recirculation returns esterification reaction tower after esterification reaction tower outlet at bottom flows out tower; The gas stream produced after reaction flows out from esterification reaction tower lower part outlet, and after purification and drying, obtains the mixed gas containing reaction product methyl nitrite successively; Described esterification reaction tower is packing tower;
2) CO carbongl group synthesis reaction: make CO and step 1) in the methyl nitrite that obtains in carbonyl synthesis reactor, there is carbonylation linked reaction oxalic dimethyl ester, and regenerate NO; NO returns step 1) in esterification reaction tower;
Wherein, the charging of described esterification reaction tower is selected from one of following manner:
Methyl alcohol, O
2flow to into reaction zone with nitrogen oxide from esterification tower top sparger;
O
2from charging between the packing section on esterification reaction tower top, and flow to into reaction zone with the methyl alcohol entered by tower distributor and nitrogen oxide.
2. continuous circulation esterification as claimed in claim 1 and carbonylation are coupled the industrial method producing dimethyl oxalate, and it is characterized in that, described nitrogen oxide is NO, NO
2, N
2o
3and N
3o
4in one or more arbitrary combination.
3. continuous circulation esterification as claimed in claim 1 and carbonylation are coupled the industrial method producing dimethyl oxalate, and it is characterized in that, the temperature of described esterification is 20 DEG C ~ 95 DEG C; Described esterification reaction pressure is 0.005-1.0MPa.
4. as the continuous circulation esterification as described in arbitrary in claim 1-3 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, the exit gas logistics of esterification reaction tower directly enters scavenging tower lower entrances, with from the scavenging agent counter current contact purifying tower top, by scavenging agent purify esterification reaction tower outlet gas stream.
5. continuous circulation esterification as claimed in claim 4 and carbonylation are coupled the industrial method producing dimethyl oxalate, and it is characterized in that, described scavenging agent is water; Described scavenging tower is tray column or packing tower, and the service temperature of scavenging tower is 10 DEG C ~ 60 DEG C.
6., as the continuous circulation esterification as described in arbitrary in claim 1-3 or 5 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, the siccative of described Dryly use selects aluminum oxide or molecular sieve; The dew-point temperature of dried gas material controls at-60 DEG C to-5 DEG C.
7. continuous circulation esterification as claimed in claim 6 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, described drying adopts one group of moisture eliminator, adopt parallel connection or series system to connect between each moisture eliminator.
8. as the continuous circulation esterification as described in arbitrary in claim 1-3,5 or 7 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, described carbonyl synthesis reactor is the reactor of single reactor or multiple employing parallel connection or series system connection.
9. continuous circulation esterification as claimed in claim 8 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, the temperature in controlling carbonyl synthesis reactor is 80 DEG C ~ 165 DEG C; Pd/Al is loaded in carbonyl synthesis reactor
2o
3catalyzer, temperature of reaction controls at 110 DEG C ~ 195 DEG C, and reaction pressure controls at 0.1 ~ 1.0MPa.
10. as the continuous circulation esterification as described in arbitrary in claim 1-3,5,7 or 9 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, the outlet streams of carbonyl synthesis reactor isolates the thick product of dimethyl oxalate after thick reactor product cooler cooling; Noncondensable gas enters Methanol Wash Column and isolate NO after methanol wash, and circulation returns esterification reaction tower.
11. continuous circulation esterifications as claimed in claim 10 and carbonylation are coupled the industrial method producing dimethyl oxalate, it is characterized in that, enter dimethyl oxalate knockout tower, isolate methyl alcohol and dimethyl oxalate through the isolated liquid stream of Methanol Wash Column.
12. 1 kinds of industrial methods producing methyl nitrite, comprise the steps: to make methyl alcohol, O
2with nitrogen oxide and the reaction zone flow to into esterification reaction tower, and carry out reaction and generate methyl nitrite; The liquid stream produced after reaction cools through water cooler the reaction zone that recirculation returns esterification reaction tower after esterification reaction tower outlet at bottom flows out tower; The gas stream produced after reaction flows out from esterification reaction tower lower part outlet, and after purification and drying, obtains methyl nitrite successively; Described esterification reaction tower is packing tower;
Wherein, the charging of described esterification reaction tower is selected from one of following manner:
Methyl alcohol, O
2flow to into reaction zone with nitrogen oxide from esterification tower top sparger;
O
2from charging between the packing section on esterification reaction tower top, and flow to into reaction zone with the methyl alcohol entered by tower distributor and nitrogen oxide.
13. industrial methods producing methyl nitrite as claimed in claim 12, it is characterized in that, described nitrogen oxide is NO, NO
2, N
2o
3and N
3o
4in one or more arbitrary combination.
14. industrial methods producing methyl nitrite as claimed in claim 12, it is characterized in that, the temperature of described esterification is 20 DEG C ~ 95 DEG C; Described esterification reaction pressure is 0.005-1.0MPa.
15. as the industrial method of the production methyl nitrite as described in arbitrary in claim 12-14, it is characterized in that, the exit gas logistics of esterification reaction tower directly enters scavenging tower lower entrances, with from the scavenging agent counter current contact purifying tower top, by scavenging agent purify esterification outlet gas stream.
16. industrial methods producing methyl nitrite as claimed in claim 15, it is characterized in that, the siccative of described Dryly use selects aluminum oxide or molecular sieve; The dew-point temperature of dried gas material controls at-60 DEG C to-5 DEG C.
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| CN109400480B (en) * | 2017-08-18 | 2022-01-04 | 上海浦景化工技术股份有限公司 | Method and equipment for preparing methyl nitrite |
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| CN101993366A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing oxalate by using CO gaseous phase process |
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| CN101993366A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing oxalate by using CO gaseous phase process |
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