CN106748785A - Waste water treatment process and system in a kind of synthesis gas preparing ethylene glycol technique - Google Patents
Waste water treatment process and system in a kind of synthesis gas preparing ethylene glycol technique Download PDFInfo
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- CN106748785A CN106748785A CN201611153493.8A CN201611153493A CN106748785A CN 106748785 A CN106748785 A CN 106748785A CN 201611153493 A CN201611153493 A CN 201611153493A CN 106748785 A CN106748785 A CN 106748785A
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- Prior art keywords
- methyl nitrite
- gas
- nitric acid
- regenerative response
- response kettle
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 95
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 95
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000008569 process Effects 0.000 title claims abstract description 26
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 299
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 140
- 230000009719 regenerative response Effects 0.000 claims abstract description 102
- 239000007789 gas Substances 0.000 claims abstract description 94
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 94
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 93
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 238000004821 distillation Methods 0.000 claims abstract description 55
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 150000004702 methyl esters Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 241000628997 Flos Species 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000010701 ester synthesis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LRMHVVPPGGOAJQ-UHFFFAOYSA-N methyl nitrate Chemical compound CO[N+]([O-])=O LRMHVVPPGGOAJQ-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFNKLDDSWHOKLQ-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C(=O)O)(=O)O OFNKLDDSWHOKLQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 235000010357 aspartame Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
Abstract
The invention belongs to synthesis gas preparing ethylene glycol technology field, and in particular to waste water treatment process and system in a kind of synthesis gas preparing ethylene glycol technique.In the present invention, from methyl nitrite synthesis reactor comprising methyl alcohol, the liquid of nitric acid and the gas comprising nitrogen oxides from dimethyl oxalate synthesis reactor, carry out reaction generation methyl nitrite into methyl nitrite regenerative response kettle；The gas of methyl nitrite regenerative response kettle is passed through dimethyl oxalate synthesis technique recycle compressor, eventually enters into dimethyl oxalate synthesis reactor；The liquid feeding methanol distillation column of methyl nitrite regenerative response kettle, reclaims methyl alcohol；After processing the liquid for obtaining feeding nitric acid concentration tower concentration through methanol distillation column, methyl nitrite regenerative response kettle is back to.The present invention makes full use of each technique advantage in itself, and the nitric acid recovery that the side reaction of synthesis gas preparing ethylene glycol technique is generated makes whole technological process more economically reliable, and can realize the zero-emission of nitric acid into methyl nitrite.
Description
Technical field
The invention belongs to synthesis gas preparing ethylene glycol technology field, and in particular in a kind of synthesis gas preparing ethylene glycol technique
Waste water treatment process and system.
Background technology
In existing industrial technology, synthesis gas preparing ethylene glycol technique is generally using the reaction life of nitric oxide, oxygen and methyl alcohol
Into methyl nitrite, then intermediate product dimethyl oxalate is generated by methyl nitrite and reaction of carbon monoxide, then by hydrogenation
Obtain ethylene glycol product, and in synthesizing the reaction system of methyl nitrite, there is a kind of side reaction for generating nitric acid.There is patent table
Bright use return again to lactate synthesis reactor after heat exchange outside extraction tower reactor liquid column, by removing reaction heat, reduces tower body temperature
To improve the degree that methyl nitrite synthetic reaction is carried out, but the concentration of nitric acid of methyl nitrite synthesis reactor outlet is still
It is higher.
Patent CN1445208A increased tank reactor in the bottom of traditional methyl nitrite distillation column reactor, lead to
Cross the nitric oxide gas and part accessory substance nitric acid reaction generation nitrous for extracting a part of destilling tower bottom liquid and input
Sour methyl esters, to improve the yield of methyl nitrite.However, the concentration of nitric acid for wanting to make tank reactor to export drop to it is sufficiently low,
Need in the form of many tank reactor series connection, along with the limitation of device fabrication, the treating capacity of tank reactor is certain,
If using very many Large Copacity tank reactors, operation difficulty is higher, and floor space is big, and economy is relatively low.Grind at present
The person of studying carefully using catalyst carry out nitric acid recovery methyl nitrite also achieve correlation breakthrough, such as patent CN104860276A, but
The concentration of nitric acid exported after reaction can be higher than still 0.1%, and cost, life-span of catalyst being related in production process etc. asks
Topic, can also increase ethylene glycol production cost.
The content of the invention
In order to overcome the problems of in the prior art, it is an object of the invention to provide a kind of synthesis gas preparing ethylene glycol
Waste water treatment process and system in technique.
To achieve these goals and other related purposes, the present invention is adopted the following technical scheme that：
A kind of the first aspect of the present invention, there is provided waste water treatment process in synthesis gas preparing ethylene glycol technique, including following step
Suddenly：
(1) synthesizing with from dimethyl oxalate comprising methyl alcohol, the liquid of nitric acid from methyl nitrite synthesis reactor
The gas comprising nitrogen oxides of reactor, reaction generation methyl nitrite is carried out into methyl nitrite regenerative response kettle；
(2) gas of methyl nitrite regenerative response kettle is passed through dimethyl oxalate synthesis technique recycle compressor, finally enters
Enter dimethyl oxalate synthesis reactor；
(3) the liquid feeding methanol distillation column of methyl nitrite regenerative response kettle, reclaims methyl alcohol；Processed through methanol distillation column
After the liquid feeding nitric acid concentration tower concentration of acquisition, methyl nitrite regenerative response kettle is back to.
In methyl nitrite synthesis reactor, the unstrpped gas containing nitrogen oxides reacts with methyl alcohol, and generation is sub-
Methyl nitrate, while generating nitric acid with side reaction.
Therefore, the liquid from methyl nitrite synthesis reactor includes methyl alcohol and nitric acid.Further, from nitrous acid
The liquid of methyl esters synthesis reactor includes methyl alcohol, water and nitric acid.
Preferably, from methyl nitrite synthesis reactor comprising in methyl alcohol, the liquid of nitric acid, the mass fraction of nitric acid
It is 1~12wt%.Preferably, the mass fraction of nitric acid is 1~6wt%.Preferably, the mass fraction of nitric acid is 6~12wt%.
Preferably, from methyl nitrite synthesis reactor comprising in methyl alcohol, the liquid of nitric acid, the mass fraction of methyl alcohol
It is 60~69wt%.
Nitrogen oxides (NOx) it is selected from NO, NO2、N2O3And N2O4In one or more.
The gas comprising nitrogen oxides from dimethyl oxalate synthesis reactor contains nitrogen oxides, nitrogen, an oxidation
Carbon and methyl nitrite.
Preferably, the gas comprising nitrogen oxides from dimethyl oxalate synthesis reactor contain nitric oxide, nitrogen,
Carbon monoxide and methyl nitrite.
Preferably, in step (1), the temperature control of methyl nitrite regenerative response kettle is at 30~100 DEG C.Preferably, it is sub-
The temperature control of methyl nitrate regenerative response kettle is at 30~60 DEG C.The temperature control of methyl nitrite regenerative response kettle 60~
100℃。
Preferably, in step (1), the Stress control of methyl nitrite regenerative response kettle is in 1.1~6barA.Preferably, it is sub-
The Stress control of methyl nitrate regenerative response kettle is in 1.1~2.1barA.Preferably, the pressure of methyl nitrite regenerative response kettle
Control is in 2.1~6barA.
Preferably, in step (2), the gas of methyl nitrite regenerative response kettle is first passed through gas-liquid separator carries out gas-liquid point
From the gas phase after separation is passed through dimethyl oxalate synthesis technique recycle compressor, and the liquid phase after separation flow to methyl nitrite certainly
Regenerative response kettle.
Preferably, in step (2), the gas of methyl nitrite regenerative response kettle generation is to include nitrogen, carbon monoxide, one
The gaseous mixture of nitrogen oxide and methyl nitrite.
Preferably, in step (3), recovered overhead methyl alcohol, and discharge fixed gas.
Preferably, in step (3), the tower top temperature of methanol distillation column is controlled at 60~61 DEG C.The tower top of methanol distillation column
Stress control is in 1.1barA.The bottom temperature of methanol distillation column is controlled at 103~104 DEG C.
Preferably, in step (3), the aqueous solution feeding nitric acid concentration tower of methanol distillation column tower reactor, nitric acid concentration tower tower top
Recycle-water, the salpeter solution after the concentration of nitric acid concentration tower tower reactor returns to methyl nitrite regenerative response kettle.
Preferably, in step (3), the tower top pressure of nitric acid concentration tower is 1.05barA.The bottom temperature of nitric acid concentration tower
It is 101.3~104.6 DEG C.
The second aspect of the present invention, there is provided the system of waste water treatment process in synthesis gas preparing ethylene glycol technique, including nitrous
Sour methyl esters regenerative response kettle, methanol distillation column and nitric acid concentration tower；The methyl nitrite regenerative response kettle respectively with nitrous acid
Methyl esters synthesis reactor, dimethyl oxalate synthesis reactor, dimethyl oxalate synthesis technique recycle compressor and methanol distillation column
Connection；Dimethyl oxalate synthesis technique recycle compressor is connected with dimethyl oxalate synthesis reactor；Methanol distillation column and nitric acid
Concentration tower is connected；Nitric acid concentration tower is connected with methyl nitrite regenerative response kettle.
Preferably, the system also includes gas-liquid separator, and the methyl nitrite regenerative response kettle (1) is by gas-liquid point
It is connected with dimethyl oxalate synthesis technique recycle compressor from device.
Further, the charging aperture of the gas-liquid separator connects with the gas phase discharging opening of methyl nitrite regenerative response kettle
Connect, the gas phase discharging opening of the gas-liquid separator is connected with dimethyl oxalate recycle compressor, the liquid phase of the gas-liquid separator
Discharging opening is connected with methyl nitrite regenerative response kettle.
Preferably, the methyl nitrite regenerative response kettle is provided with temperature survey and control device.
Preferably, the methyl nitrite regenerative response kettle is provided with pressure measxurement and control device.
Preferably, the methyl nitrite regenerative response kettle is provided with Gas distribution device, and the methyl nitrite regeneration is anti-
Kettle is answered to be connected with dimethyl oxalate synthesis reactor by the Gas distribution device.
Preferably, the tower top of the methanol distillation column is provided with methanol recovery device.
Preferably, the tower top of the methanol distillation column is provided with fixed gas floss hole.
Preferably, the tower reactor of the methanol distillation column is provided with liquid phase discharging opening.
Preferably, the methanol distillation column is provided with temperature survey and control device.
Preferably, the methanol distillation column is provided with pressure measxurement and control device.
Preferably, the tower top of the nitric acid concentration tower is provided with apparatus for recovering.
Preferably, the tower reactor of the nitric acid concentration tower is provided with liquid phase discharging opening.
Preferably, the nitric acid concentration tower is provided with temperature survey and control device.
Preferably, the nitric acid concentration tower is provided with pressure measxurement and control device.
Compared with prior art, the present invention has the advantages that：
In the present invention, from methyl nitrite synthesis reactor comprising methyl alcohol, the liquid of nitric acid with come from oxalic acid diformazan
The gas comprising nitrogen oxides of ester synthesis reaction device, reaction generation nitrous acid first is carried out into methyl nitrite regenerative response kettle
Ester；The gas of methyl nitrite regenerative response kettle is passed through dimethyl oxalate synthesis technique recycle compressor, eventually enters into oxalic acid two
Methyl esters synthesis reactor；The liquid feeding methanol distillation column of methyl nitrite regenerative response kettle, reclaims methyl alcohol；Through methanol distillation column
After processing the liquid feeding nitric acid concentration tower concentration for obtaining, methyl nitrite regenerative response kettle is back to.The present invention makes full use of
Each technique advantage, the nitric acid recovery that the side reaction of synthesis gas preparing ethylene glycol technique is generated in itself makes whole into methyl nitrite
Technological process is more economically reliable, and can realize the zero-emission of nitric acid.
Brief description of the drawings
Fig. 1：The system schematic of waste water treatment process in synthesis gas preparing ethylene glycol technique.
Reference：
1- methyl nitrite regenerative responses kettle, 2- methanol distillation columns, 3- nitric acid concentration towers.
Specific embodiment
Before the specific embodiment of the invention is further described, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that the term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than in order to limit the scope of the invention.The test method of unreceipted actual conditions in the following example,
Generally according to normal condition, or according to the condition proposed by each manufacturer.
When embodiment provides number range, it should be appreciated that except non-invention is otherwise noted, two ends of each number range
Any one numerical value can select between point and two end points.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the meaning that those skilled in the art of the present technique are generally understood that.Except the specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to prior art can also be used and this
Any method, equipment and material in the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
Unless otherwise indicated, disclosed in this invention experimental technique, detection method, preparation method using this technology lead
The routine techniques in domain, the perfect explanation in existing document of these technologies.
As shown in figure 1, in synthesis gas preparing ethylene glycol technique waste water treatment process system, including methyl nitrite regeneration is anti-
Answer kettle 1, methanol distillation column 2 and nitric acid concentration tower 3.The methyl nitrite regenerative response kettle 1 synthesizes with methyl nitrite respectively
Reactor, dimethyl oxalate synthesis reactor, dimethyl oxalate synthesis technique recycle compressor and methanol distillation column 2 are connected；Grass
Dimethyl phthalate synthesis technique recycle compressor is connected with dimethyl oxalate synthesis reactor；Methanol distillation column 2 and nitric acid concentration tower 3
Connection；Nitric acid concentration tower 3 is connected with methyl nitrite regenerative response kettle 1.
In certain embodiments of the present invention, the methyl nitrite regenerative response kettle 1 is provided with liquid phase feeding mouthful, gas phase
Charging aperture, gas phase discharging opening and liquid phase discharging opening.Liquid phase feeding mouthful and the nitrous acid first of the methyl nitrite regenerative response kettle 1
The liquid phase discharging opening connection of ester synthesis reaction device；Gas-phase feed mouthful and the oxalic acid diformazan of the methyl nitrite regenerative response kettle 1
The gas phase discharging opening connection of ester synthesis reaction device.In methyl nitrite synthesis reactor, the unstrpped gas containing nitrogen oxides,
Reacted with methyl alcohol, generate methyl nitrite, while generating nitric acid with side reaction.Therefore, synthesize from methyl nitrite
The liquid of reactor includes methyl alcohol and nitric acid.Further, the liquid from methyl nitrite synthesis reactor includes methyl alcohol, water
And nitric acid.And the gas comprising nitrogen oxides from dimethyl oxalate synthesis reactor contains nitrogen oxides, nitrogen, an oxidation
Carbon and methyl nitrite.Therefore, from methyl nitrite synthesis reactor comprising methyl alcohol, the liquid of nitric acid with come from oxalic acid two
The gas comprising nitrogen oxides of methyl esters synthesis reactor, can carry out reaction generation sub- into methyl nitrite regenerative response kettle 1
Methyl nitrate.
In certain embodiments of the present invention, the liquid comprising methyl alcohol, nitric acid from methyl nitrite synthesis reactor
In body, the mass fraction of nitric acid can be 1~12wt%.The mass fraction of nitric acid can also be 1~6wt%.The quality of nitric acid
Fraction can also be 6~12wt%.From methyl nitrite synthesis reactor comprising methyl alcohol, the liquid of nitric acid in, methyl alcohol
Mass fraction can be 60~69wt%.Nitrogen oxides (NOx) it is selected from NO, NO2、N2O3And N2O4In one or more.From grass
The gas comprising nitrogen oxides of dimethyl phthalate synthesis reactor contains nitric oxide, nitrogen, carbon monoxide and methyl nitrite.
In certain embodiments of the present invention, the methyl nitrite regenerative response kettle 1 is additionally provided with temperature survey (for example
Thermometer) and control device (such as jacket-type water-bath) and pressure measxurement (such as pressure gauge) and control device (Stress control
Valve), to control the temperature and pressure in methyl nitrite regenerative response kettle in suitable scope.For example, can be by nitrous acid first
The temperature control of ester regenerative response kettle 1 is at 30~100 DEG C.Preferably, can be by the temperature control of methyl nitrite regenerative response kettle
At 30~60 DEG C.Can also be by the temperature control of methyl nitrite regenerative response kettle 1 at 60~100 DEG C.Methyl nitrite regeneration is anti-
The pressure controllable system of kettle is answered in 1.1~6barA.Preferably, the pressure controllable system of methyl nitrite regenerative response kettle 1.1~
2.1barA.The pressure of methyl nitrite regenerative response kettle also can be controlled in 2.1~6barA.
In certain embodiments of the present invention, the methyl nitrite regenerative response kettle 1 can also be provided with Gas distribution dress
Put (such as Gas distribution pipe), the methyl nitrite regenerative response kettle 1 passes through the Gas distribution device and dimethyl oxalate
Synthesis reactor is connected.The Gas distribution device can make the gas from dimethyl oxalate synthesis reactor in methyl nitrite
It is evenly distributed in regenerative response kettle 1.
In certain embodiments of the present invention, the gas phase discharging opening and oxalic acid of the methyl nitrite regenerative response kettle 1
Dimethyl ester synthesis technique recycle compressor is connected.The gas of methyl nitrite regenerative response kettle is to include nitrogen, carbon monoxide, one
The gaseous mixture of nitrogen oxide and methyl nitrite.Thus, the gas of methyl nitrite regenerative response kettle 1 is passed through dimethyl oxalate synthesis
Process cycles compressor, eventually enters into dimethyl oxalate synthesis reactor, continues to participate in dimethyl oxalate synthetic reaction.Further
Ground, the system may also include gas-liquid separator, and the methyl nitrite regenerative response kettle 1 is by gas-liquid separator and oxalic acid two
Methyl esters synthesis technique recycle compressor is connected.Specifically, the charging aperture of the gas-liquid separator and methyl nitrite regenerative response
The gas phase discharging opening connection of kettle 1, the gas phase discharging opening of the gas-liquid separator is connected with dimethyl oxalate recycle compressor, described
The liquid phase discharging opening of gas-liquid separator is connected with methyl nitrite regenerative response kettle 1.So, methyl nitrite regenerative response kettle 1
Gas just can first be passed through gas-liquid separator and carry out gas-liquid separation, the gas phase after separation is passed through dimethyl oxalate synthesis technique and follows
Ring compressor, the liquid phase after separation flow to methyl nitrite regenerative response kettle 1 certainly.
In certain embodiments of the present invention, the liquid phase discharging opening and methyl alcohol of the methyl nitrite regenerative response kettle 1
The liquid phase feeding mouthful connection of recovery tower 2.The liquid phase discharging opening of methanol distillation column 2 is connected with the liquid phase feeding mouthful of nitric acid concentration tower 3.
The liquid phase discharging opening of nitric acid concentration tower 3 is connected with the liquid phase feeding mouthful of methyl nitrite regenerative response kettle 1.Thus, nitrous acid first
The liquid of ester regenerative response kettle 1 can send into methanol distillation column 2, reclaim methyl alcohol；The liquid for obtaining is processed through methanol distillation column to send again
After entering the concentration of nitric acid concentration tower 3, methyl nitrite regenerative response kettle 1 is back to, continues to participate in the regenerative response of methyl nitrite.
In certain embodiments of the present invention, the methanol distillation column 2 is provided with temperature survey (such as thermometer) and control
Device (such as jacket-type water-bath) processed and pressure measxurement (such as pressure gauge) and control device (such as pressure-control valve), to control
Temperature and pressure in methanol distillation column processed is in suitable scope.For example, the tower top temperature control of methanol distillation column 60~
61℃.The tower top pressure of methanol distillation column is controlled in 1.1barA.The bottom temperature of methanol distillation column is controlled at 103~104 DEG C.
The tower top of the methanol distillation column 2 can also be provided with methanol recovery device (such as condenser), for reclaiming methyl alcohol.The methyl alcohol is returned
The tower top for receiving tower 2 can also be provided with fixed gas floss hole, to discharge the on-condensible gas produced in methanol distillation column.Can be in the methyl alcohol
The tower reactor of recovery tower 2 sets liquid phase discharging opening, and processing the liquid for obtaining through the tower reactor of methanol distillation column 2 can be exported by liquid phase discharging opening
Deliver to nitric acid concentration tower 3.
In certain embodiments of the present invention, the nitric acid concentration tower 3 is provided with temperature survey (such as thermometer) and control
Device (such as jacket-type water-bath) processed and pressure measxurement (such as pressure gauge) and control device (such as pressure-control valve) are with control
Temperature and pressure in nitric acid concentration tower processed is in suitable scope.For example, the tower top pressure of nitric acid concentration tower is 1.05barA.
The bottom temperature of nitric acid concentration tower is 101.3~104.6 DEG C.The tower top of the nitric acid concentration tower 3 can also be provided with apparatus for recovering
(such as condenser), the water for reclaiming the generation of nitric acid concentration tower 3.Liquid phase discharging opening can be set in the tower reactor of nitric acid concentration tower 3,
Methyl nitrite regenerative response kettle 1 is returned for exporting the liquid after concentration.
Embodiment 1
Shown in refer to the attached drawing 1, from methyl nitrite synthesis reactor liquid out【Flow about 3.5kg/h, wherein nitric acid
Mass fraction is 6%, contains methyl alcohol 69% and water 25%】, into methyl nitrite regenerative response kettle 1, with kettle in through gas phase point
Stringing spray from dimethyl oxalate synthesis reactor exit gas【Flow is about 1.3Nm3/ h, wherein NO, N2, CO and MN
(methyl nitrite) composition is followed successively by：0.2 (v/v), 0.6 (v/v), 0.18 (v/v) and 0.02 (v/v)】, in methyl nitrite again
Generation methyl nitrite is reacted in raw reactor 1, the pressure of control regenerative response kettle 1 is about 2.1barA, and temperature is about 60 DEG C,
The gas of generation leaves regenerative response kettle 1 and enters gas-liquid separator, and the gas phase after separation send dimethyl oxalate synthesis technique to circulate
Suction port of compressor, the liquid phase after separation flow to methyl nitrite regenerative response kettle 1 certainly.
The liquid feeding methanol distillation column 2 of methyl nitrite regenerative response kettle 1, control tower top pressure is about 1.1barA, tower
About 103 DEG C of kettle temperature degree, tower top temperature is about 60 DEG C, the recovered overhead methyl alcohol of methanol distillation column 2, and discharges fixed gas, Methanol Recovery
The tower reactor solution aqueous 94.2% of tower 2, nitric acid is about 5.8%.
The tower reactor aqueous solution of nitric acid of methanol distillation column 2 sends into nitric acid concentration tower 3, and control tower top pressure is about 1.05barA, tower
Kettle temperature degree is about 103.5 DEG C, and the concentration of nitric acid after tower reactor is concentrated reaches 28.8%, is back to methyl nitrite regenerative response kettle
1 continues to react generation methyl nitrite, realizes the zero-emission of nitric acid.
Embodiment 2
Shown in refer to the attached drawing 1, from methyl nitrite synthesis reactor liquid out【Flow about 3.5kg/h, wherein nitric acid
Mass fraction is 1%, contains methyl alcohol 69% and water 30%】, into methyl nitrite regenerative response kettle 1, with kettle in through gas phase point
Stringing spray from dimethyl oxalate synthesis reactor exit gas,【Flow is about 0.5Nm3/ h, wherein NO, N2, CO and MN
Composition is followed successively by：0.2 (v/v), 0.6 (v/v), 0.18 (v/v) and 0.02 (v/v)】, generation is reacted in regenerative response kettle 1 sub-
Methyl nitrate, the pressure of control regenerative response kettle 1 is about 6barA, and temperature is about 100 DEG C, and the gas of generation leaves regenerative response
Kettle 1 enters gas-liquid separator, and the gas phase after separation send dimethyl oxalate synthesis technique recycle compressor entrance, the liquid phase after separation
From flowing to methyl nitrite regenerative response kettle 1.
The liquid feeding methanol distillation column 2 of methyl nitrite regenerative response kettle 1, control tower top pressure is about 1.1barA, tower
About 104 DEG C of kettle temperature degree, tower top temperature is about 61 DEG C, the recovered overhead methyl alcohol of methanol distillation column 2, and discharges fixed gas, Methanol Recovery
Tower tower reactor solution aqueous 99.3%, nitric acid is about 0.7%.
The tower reactor aqueous solution of nitric acid of methanol distillation column 2 sends into nitric acid concentration tower 3, and control tower top pressure is about 1.05barA, tower
Kettle temperature degree is about 101.3 DEG C, and the concentration of nitric acid after tower reactor is concentrated reaches 3.6%, is back to methyl nitrite regenerative response kettle 1
Continue to react generation methyl nitrite, realize the zero-emission of nitric acid.
Embodiment 3
Shown in refer to the attached drawing 1, from methyl nitrite synthesis reactor liquid out【Flow about 3.5kg/h, wherein nitric acid
Mass fraction is 12%, contains methyl alcohol 60% and water 28%】, into methyl nitrite regenerative response kettle 1, with kettle in through gas phase point
Stringing spray from dimethyl oxalate synthesis reactor exit gas【Flow is about 2.4Nm3/ h, wherein NO, N2, CO and MN groups
Into being followed successively by：0.2 (v/v), 0.6 (v/v), 0.18 (v/v) and 0.02 (v/v)】Generation nitrous acid is reacted in regenerative response kettle 1
Methyl esters, the pressure of control regenerative response kettle 1 is about 1.1barA, and temperature is about 30 DEG C, and the gas of generation leaves regenerative response kettle 1
Into gas-liquid separator, the gas phase after separation send dimethyl oxalate synthesis technique recycle compressor entrance, and the liquid phase after separation is certainly
It flow to methyl nitrite regenerative response kettle 1.
The liquid feeding methanol distillation column 2 of methyl nitrite regenerative response kettle 1, control tower top pressure is about 1.1barA, tower
About 103 DEG C of kettle temperature degree, tower top temperature is about 61 DEG C, the recovered overhead methyl alcohol of methanol distillation column 2, and discharges fixed gas, Methanol Recovery
Tower tower reactor solution aqueous 90.4%, nitric acid is about 9.6%.
Methanol distillation column tower reactor aqueous solution of nitric acid sends into nitric acid concentration tower 3, and control tower top pressure is about 1.05barA, tower reactor
Temperature is about 104.6 DEG C, and the concentration of nitric acid after tower reactor is concentrated reaches 47.7%, is back to methyl nitrite regenerative response kettle 1
Continue to react generation methyl nitrite, realize the zero-emission of nitric acid.
The above, only presently preferred embodiments of the present invention, it is not any to the present invention in form and substantial limitation,
It should be pointed out that for those skilled in the art, on the premise of the inventive method is not departed from, can also make
Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations for developing, are Equivalent embodiments of the invention；Meanwhile, it is all according to substantial technological pair of the invention
The variation, modification and evolution of any equivalent variations that above-described embodiment is made, still fall within the scope of technical scheme
It is interior.
Claims (18)
1. waste water treatment process in a kind of synthesis gas preparing ethylene glycol technique, comprises the following steps：
(1) from methyl nitrite synthesis reactor comprising methyl alcohol, the liquid of nitric acid with come from dimethyl oxalate synthetic reaction
The gas comprising nitrogen oxides of device, reaction generation methyl nitrite is carried out into methyl nitrite regenerative response kettle；
(2) gas of methyl nitrite regenerative response kettle is passed through dimethyl oxalate synthesis technique recycle compressor, eventually enters into grass
Dimethyl phthalate synthesis reactor；
(3) the liquid feeding methanol distillation column of methyl nitrite regenerative response kettle, reclaims methyl alcohol；Processed through methanol distillation column and obtained
Liquid feeding nitric acid concentration tower concentration after, be back to methyl nitrite regenerative response kettle.
2. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that from nitrous
Sour methyl esters synthesis reactor comprising in methyl alcohol, the liquid of nitric acid, the mass fraction of nitric acid is 1~12wt%.
3. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that from nitrous
Sour methyl esters synthesis reactor comprising in methyl alcohol, the liquid of nitric acid, the mass fraction of methyl alcohol is 60~69wt%.
4. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that the nitrogen oxygen
Compound is selected from NO, NO2、N2O3And N2O4In one or more.
5. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that from oxalic acid
The gas comprising nitrogen oxides of dimethyl ester synthesis reactor contains nitric oxide, nitrogen, carbon monoxide and methyl nitrite.
6. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that step (1)
In, the temperature control of methyl nitrite regenerative response kettle is at 30~100 DEG C.
7. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that step (1)
In, the Stress control of methyl nitrite regenerative response kettle is in 1.1~6barA.
8. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that step (2)
In, the gas of methyl nitrite regenerative response kettle generation is first passed through gas-liquid separator carries out gas-liquid separation, and the gas phase after separation is led to
Enter dimethyl oxalate synthesis technique recycle compressor, the liquid phase after separation flow to methyl nitrite regenerative response kettle certainly.
9. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that step (2)
In, the gas of methyl nitrite regenerative response kettle generation is to include mixing for nitrogen, carbon monoxide, nitric oxide and methyl nitrite
Close gas.
10. waste water treatment process in synthesis gas preparing ethylene glycol technique according to claim 1, it is characterised in that step (3)
In, the recovered overhead methyl alcohol of methanol distillation column, and discharge fixed gas.
Waste water treatment process in 11. synthesis gas preparing ethylene glycol techniques according to claim 1, it is characterised in that step (3)
In, the aqueous solution feeding nitric acid concentration tower of methanol distillation column tower reactor, nitric acid concentration tower recovered overhead water, nitric acid concentration tower tower reactor is dense
Salpeter solution after contracting returns to methyl nitrite regenerative response kettle.
Waste water treatment process in 12. synthesis gas preparing ethylene glycol techniques according to claim 1, it is characterised in that also include
Any one of following characteristics are multinomial：(1) tower top temperature of methanol distillation column is controlled at 60~61 DEG C；And/or (2) methyl alcohol is returned
The tower top pressure for receiving tower is controlled in 1.1barA；And/or the bottom temperature of (3) methanol distillation column is controlled at 103~104 DEG C；With/
Or the tower top pressure of (4) nitric acid concentration tower is 1.05barA；And/or the bottom temperature of (5) nitric acid concentration tower be 101.3~
104.6℃。
The system of waste water treatment process in a kind of 13. synthesis gas preparing ethylene glycol techniques, including methyl nitrite regenerative response kettle, first
Alcohol recovery tower and nitric acid concentration tower；The methyl nitrite regenerative response kettle respectively with methyl nitrite synthesis reactor, oxalic acid
The connection of dimethyl ester synthesis reactor, dimethyl oxalate synthesis technique recycle compressor and methanol distillation column；Dimethyl oxalate synthesizes
Process cycles compressor is connected with dimethyl oxalate synthesis reactor；Methanol distillation column is connected with nitric acid concentration tower；Nitric acid is concentrated
Tower is connected with methyl nitrite regenerative response kettle.
14. systems according to claim 13, it is characterised in that the system also includes gas-liquid separator, the nitrous
Sour methyl esters regenerative response kettle (1) is connected by gas-liquid separator with dimethyl oxalate synthesis technique recycle compressor.
15. systems according to claim 14, it is characterised in that the charging aperture and methyl nitrite of the gas-liquid separator
The gas phase discharging opening connection of regenerative response kettle, gas phase discharging opening and the dimethyl oxalate recycle compressor of the gas-liquid separator connect
Connect, the liquid phase discharging opening of the gas-liquid separator is connected with methyl nitrite regenerative response kettle.
16. systems according to claim 13, it is characterised in that the tower top of the methanol distillation column is provided with Methanol Recovery dress
Put.
17. systems according to claim 13, it is characterised in that the tower top of the nitric acid concentration tower is provided with Water Sproading dress
Put.
18. systems according to claim 13, it is characterised in that also including any one of following characteristics or multinomial：(1)
The methyl nitrite regenerative response kettle is provided with temperature survey and control device；(2) the methyl nitrite regenerative response kettle sets
There are pressure measxurement and control device；(3) the methyl nitrite regenerative response kettle is provided with Gas distribution device, the nitrous acid first
Ester regenerative response kettle is connected by the Gas distribution device with dimethyl oxalate synthesis reactor；(4) methanol distillation column
Tower top be provided with fixed gas floss hole；(5) tower reactor of the methanol distillation column is provided with liquid phase discharging opening；(6) Methanol Recovery
Tower is provided with temperature survey and control device；(7) methanol distillation column is provided with pressure measxurement and control device；(8) nitric acid
The tower reactor of concentration tower is provided with liquid phase discharging opening；(9) nitric acid concentration tower is provided with temperature survey and control device；(10) nitre
Sour concentration tower is provided with pressure measxurement and control device.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264684A (en) * | 2018-11-07 | 2019-01-25 | 宁波中科远东催化工程技术有限公司 | Nitric acid reclaiming clean technique |
| CN109456197A (en) * | 2018-10-26 | 2019-03-12 | 新疆天智辰业化工有限公司 | A kind of method that low concentration nitric acid solution recycles in calcium carbide stove exhaust preparing ethylene glycol |
| CN109734559A (en) * | 2019-03-05 | 2019-05-10 | 西南化工研究设计院有限公司 | The energy saving technique and system of nitrous acid ester regeneration by-product dust technology in ethylene glycol preparation |
| WO2020103556A1 (en) * | 2018-11-20 | 2020-05-28 | 上海浦景化工技术股份有限公司 | Nitric acid reduction conversion process |
| CN112759518A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
| WO2022110871A1 (en) * | 2020-11-30 | 2022-06-02 | 南京延长反应技术研究院有限公司 | Enhanced micro-interface reaction system and method for preparing ethylene glycol by oxalate method |
| RU2781548C1 (en) * | 2018-11-20 | 2022-10-13 | Пуцзин Кемикал Индастри Ко., Лтд | Method for conversion of nitric acid by reduction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373925A (en) * | 2012-04-27 | 2013-10-30 | 上海浦景化工技术有限公司 | Preparation method for methyl nitrite |
| CN104098441A (en) * | 2014-06-05 | 2014-10-15 | 上海戊正工程技术有限公司 | Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation |
| CN205188178U (en) * | 2015-10-20 | 2016-04-27 | 上海华谊能源化工有限公司 | Methyl nitrite's regenerating unit system in synthetic gas system ethylene glycol technology |
| CN205188177U (en) * | 2015-10-20 | 2016-04-27 | 上海华谊能源化工有限公司 | Methyl nitrite's regenerating unit system in synthetic gas system ethylene glycol technology |
-
2016
- 2016-12-14 CN CN201611153493.8A patent/CN106748785A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373925A (en) * | 2012-04-27 | 2013-10-30 | 上海浦景化工技术有限公司 | Preparation method for methyl nitrite |
| CN104098441A (en) * | 2014-06-05 | 2014-10-15 | 上海戊正工程技术有限公司 | Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation |
| CN205188178U (en) * | 2015-10-20 | 2016-04-27 | 上海华谊能源化工有限公司 | Methyl nitrite's regenerating unit system in synthetic gas system ethylene glycol technology |
| CN205188177U (en) * | 2015-10-20 | 2016-04-27 | 上海华谊能源化工有限公司 | Methyl nitrite's regenerating unit system in synthetic gas system ethylene glycol technology |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456197A (en) * | 2018-10-26 | 2019-03-12 | 新疆天智辰业化工有限公司 | A kind of method that low concentration nitric acid solution recycles in calcium carbide stove exhaust preparing ethylene glycol |
| CN109456197B (en) * | 2018-10-26 | 2021-09-03 | 新疆天智辰业化工有限公司 | Method for recycling low-concentration nitric acid solution in process of preparing ethylene glycol from calcium carbide furnace tail gas |
| CN109264684A (en) * | 2018-11-07 | 2019-01-25 | 宁波中科远东催化工程技术有限公司 | Nitric acid reclaiming clean technique |
| WO2020103556A1 (en) * | 2018-11-20 | 2020-05-28 | 上海浦景化工技术股份有限公司 | Nitric acid reduction conversion process |
| AU2019382545B2 (en) * | 2018-11-20 | 2022-03-10 | Pujing Chemical Industry Co., Ltd | Nitric acid reduction conversion process |
| RU2781548C1 (en) * | 2018-11-20 | 2022-10-13 | Пуцзин Кемикал Индастри Ко., Лтд | Method for conversion of nitric acid by reduction |
| CN109734559A (en) * | 2019-03-05 | 2019-05-10 | 西南化工研究设计院有限公司 | The energy saving technique and system of nitrous acid ester regeneration by-product dust technology in ethylene glycol preparation |
| CN112759518A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
| CN112759518B (en) * | 2019-10-21 | 2023-04-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
| WO2022110871A1 (en) * | 2020-11-30 | 2022-06-02 | 南京延长反应技术研究院有限公司 | Enhanced micro-interface reaction system and method for preparing ethylene glycol by oxalate method |
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