CN109748827A - The process of continuous synthesis dimethyl suflfate - Google Patents
The process of continuous synthesis dimethyl suflfate Download PDFInfo
- Publication number
- CN109748827A CN109748827A CN201910108585.1A CN201910108585A CN109748827A CN 109748827 A CN109748827 A CN 109748827A CN 201910108585 A CN201910108585 A CN 201910108585A CN 109748827 A CN109748827 A CN 109748827A
- Authority
- CN
- China
- Prior art keywords
- tower
- dimethyl
- esterification
- section
- dimethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of process of continuous synthesis dimethyl suflfate, two kinds of raw materials of sulfur trioxide and dimethyl ether are successively absorbed in the different section areas of three-level esterification reaction tower by thick dimethyl suflfate, it contacts and reacts generation dimethyl suflfate, dimethyl sulfate product and byproduct methyl-hydrogen-sulfate monomethyl-sulfate are obtained by degassing and rectifying separation process, including continuous synthetic reaction process and degassing and distillation process: continuous synthetic reaction process occurs in three-level esterification reaction tower, and reaction tower is divided into SO3 absorber portion, dimethyl ether DME absorbs esterification section, the area aging Duan Sangeduan.The dimethyl ether DME of the three-level esterification reaction tower absorbs esterification section and aging intersegmental part is provided with many places tower grade component, is distributed in the tower body inner wall in section area, the fan-shaped structure of tower grade component.The process process that the present invention prepares dimethyl suflfate is simple, reduces energy consumption, and cost of reducing investment outlay has prevented the appearance of the production problem such as run, drip, leak, also to realize that large-scale industrial production provides safeguard, dimethyl sulfate product purity is high.
Description
Technical field
This patent disclosure relates generally to the synthetic technology of dimethyl suflfate, relates more particularly to a kind of dimethyl suflfate and continuously synthesize
Process.
Background technique
Dimethyl suflfate is a kind of important chemical industry centre product, methylating agent, in pharmaceutical sector, agricultural, textile industry, building
It suffers from and is widely applied in a variety of industries such as industry, petrochemical industry, paper industry, food industry, household chemicals production.For
The synthetic method of dimethyl suflfate more generally applies SO at present3Esterification occurs so that sulfuric acid two is made with dimethyl ether
Methyl esters.
Patent CN 1272489A disclose it is a kind of with sulphur be starting material extracting sulfuric acid dimethyl ester method: first with
SO is made in sulphur3, then SO is absorbed with dimethyl suflfate3And it is enriched with to 15~25g/100g, then react extracting sulfuric acid with dimethyl ether
Dimethyl ester.Patent CN 200810048926.2 discloses the production technology of preparing dimethyl sulfate by composite acid through catalytic dehydration: using
Complex acid catalyst catalysis methanol, which is dehydrated, is made gas of dimethyl ether, reacts life with the dimethyl suflfate rich solution for absorbing sulfur trioxide
At dimethyl suflfate crude product, qualified dimethyl suflfate finished product is obtained through being evaporated under reduced pressure.Patent CN 1041307C discloses one kind
The method and apparatus that dry air combustion sulphur prepares sulfuric ester: air and sulphur effect are eventually converted into SO3Gas uses dimethyl sulfate
Ester makees lyosoption, then is esterified Sulphuric acid dimethyl ester with dimethyl ether.103570590 B of patent CN discloses a kind of production sulfuric acid
The equipment of dimethyl ester: including esterification reaction tower, degassing tower, rectifying column, the serialization of production process is realized.Patent CN
103566851B discloses a kind of dimethyl suflfate esterification reaction tower, to increase dimethyl ether and three in dimethyl suflfate esterification process
The long-time of sulfur oxide contacts, so that sulfur trioxide be enable to react completely, reduces product acidity.
The synthesis technology of above-mentioned synthesis dimethyl suflfate has in common that reactant sulfur trioxide and dimethyl ether exist
Absorbing reaction process in dimethyl suflfate carries out step by step in two operating units: sulfur trioxide was in dimethyl suflfate before this
Absorption (our products be referred to as burnt ester), then burnt ester, which absorbs dimethyl ether and esterification occurs, generates dimethyl suflfate.This is
Because dimethyl ether is inflammable gas, sulfur trioxide is strong oxidizer, and the two is dissolved in dimethyl suflfate simultaneously and esterification occurs
Explosive reaction may be led to because of hot-spot, cause safety accident.
Summary of the invention
For above-mentioned technological deficiency, the present invention uses PROCESS COUPLING technology, the novel three stage countercurrents ester of creative use
Change reaction tower.According to the fluid behaviour and kinetic parameter of the intracorporal gas of tower and liquid, ester is absorbed in the dimethyl ether DME in tower
Change section, the design of aging section is mounted with many places sector tower grade component.The ingenious utilization of fan-shaped component simultaneously enhances top-down liquid
Aerodynamic force from bottom to top can not stall under the power effect of this gas-liquid cycle, continues to strengthen this part and follow
Ring and mixability realize gas-liquid convection and local circulation so as to improve the distribution of gas and liquid, pass to realize reinforcing
The effect of matter and heat transfer causes to react there is a situation where explosive to prevent hot-spot；In addition, fan blades have cutting,
The effect of bubble crushing.The optimization design of this novel three-level esterification reaction tower of the present invention makes with a reaction tower instead of biography
The SO of system3Two operating units in absorption tower and absorption of dimethyl ether esterifier.The setting of component can effectively facilitate reactant three
The complete reaction of sulfur oxide keeps dimethyl sulfate product (>99.5%) with high purity, and acidity is low (<0.03%).Entire technique simplifies
The technological process of production of dimethyl suflfate, reduces energy consumption, cost of reducing investment outlay；The production technology of serialization prevented run,
The appearance of production problem such as emit, drip, leaking, also to realize that large-scale industrial production provides safeguard.
Specifically, the present invention provides a kind of process that dimethyl suflfate continuously synthesizes: sulfur trioxide and dimethyl ether two
Kind raw material is successively absorbed in the different section areas of three-level esterification reaction tower by thick dimethyl suflfate, contacts and reacts generation dimethyl sulfate
Ester obtains the dimethyl sulfate product and byproduct methyl-hydrogen-sulfate monomethyl-sulfate of high-purity by degassing and rectifying separation process.Specifically
Method is as follows:
(1) continuous synthetic reaction process: the process occurs in three-level esterification reaction tower 101, and reaction tower 101 divides for SO3
Absorber portion (101-1 sections of areas), dimethyl ether (DME) absorb esterification section (101-2 sections of areas), aging section (101-3 sections of areas) three areas Ge Duan.
Thick dimethyl suflfate continuously enters SO by being located at the entrance on tower top3Absorber portion 101-1, it is uniform through liquid distribution trough 101-10
It is dispersed to packing layer.Conversion gas is entered in tower body by being located at the entrance of the bottom absorber portion 101-1 Duan Qu, through gas distributor
101-11 is evenly dispersed, and when it is upwardly through filler laminar flow, and thick dimethyl suflfate is gas-liquid conversed contacts, and converts in gas
Sulfur trioxide is dissolved, absorbs, and forms burnt ester；Other inert gases pass through tower top after demister 101-9 separates entrainment
Gas vent be discharged into subsequent vent gas treatment workshop section.Burnt ester is through outlet 101-5 and entrance 101-6 by absorber portion (101-1) quilt
It is transferred to dimethyl ether DME and absorbs esterification section (101-2).DME absorbs the bottom inlet in section 101-2 sections of area of esterification from dimethyl ether DME
It into tower, is uniformly dispersed through 101-4 gas distributor, is dissolved, absorbs by the burnt ester in section area, in part DME and burnt ester
SO3It contacts with each other and esterification occurs and generate dimethyl suflfate.Dimethyl ether DME absorbs the reaction solution in section 101-2 sections of area of esterification
Section 101-2 sections of area of esterification is absorbed by dimethyl ether DME through outlet 101-7 and entrance 101-8 and is transferred to 101-3 sections of areas of aging section,
It further contacts and is esterified in 101-3 sections of areas of aging section in the dimethyl ether DME absorption section 101-2 sections of unreacted material in area of esterification
Reaction generates dimethyl suflfate.
(2) degassing and distillation process: contain unreacted original in the dimethyl suflfate reaction solution from esterification reaction tower 101
Expect dimethyl ether DME and sulfur trioxide SO3.Reaction solution enters degassing tower 102 by esterification reaction tower 101, and degassing tower is added by steam
Heat, by DME and SO unreacted in dimethyl suflfate reaction solution3It separates, and returns to the dimethyl ether of esterification reaction tower 101
DME absorbs section 101-2 sections of area of esterification, continues to react.Dimethyl suflfate a part after degassed is transferred to rectifying column
Rectification under vacuum is carried out in 103, and the SO of esterification reaction tower 101 is returned after a part of water cooled device 106-2 condensing heat-exchange3Absorber portion
101-1 sections of areas.The cooling rear portion of the water cooled device 106-3 of the dimethyl suflfate steam on 103 tower top of rectifying column return tower body after
Continuous rectifying, a part are produced as product, obtain the dimethyl sulfate product of high-purity；Vacuum system fixed gas is discharged from tower top
After remove exhaust gas processing device.Rectifying tower reactor obtains byproduct methyl-hydrogen-sulfate monomethyl-sulfate.
The dimethyl ether DME of the three-level esterification reaction tower absorbs setting inside the 101-3 sections of areas esterification section 101-2 and aging section
There is many places tower grade component, is distributed in the tower body inner wall in section area.
In a preferable example, the fan-shaped structure of tower grade component.The ingenious utilization of fan-shaped component simultaneously enhances from top to bottom
Liquid and aerodynamic force from bottom to top can not stall under the power effect of this gas-liquid cycle, further enhance this
Kind local circulation and mixability realize gas-liquid convection and local circulation, to realize so as to improve the distribution of gas and liquid
Strengthen the effect of mass transfer and heat transfer, leads to that there is a situation where bursts to react to prevent hot-spot；In addition, fan blades has
There are cutting, bubble crushing.The optimization design of this novel three-level esterification reaction tower of the embodiment of the present invention makes with one
A reaction tower is instead of traditional SO3Two operating units in absorption tower and absorption of dimethyl ether esterifier.The setting of component can
The complete reaction for effectively facilitating reactant sulfur trioxide keeps dimethyl sulfate product with high purity (>99.5%), acidity it is low (<
0.03%).Entire technique simplifies the technological process of production of dimethyl suflfate, reduces energy consumption, cost of reducing investment outlay；Serialization
Production technology prevented run, drip, leak etc. production problem appearance, also for realize large-scale industrial production provide safeguard.
In one example, the Temperature Distribution of the esterification reaction tower 101 are as follows: SO330~70 DEG C of absorber portion (101-1),
Dimethyl ether DME absorb esterification 70~85 DEG C of section (101-2), 85~95 DEG C of aging section (101-3), operating pressure be 0.1~
0.2MPa.Wherein SO3101-1 sections of area setting condensing heat exchanger 106-1 of absorber portion remove partial heat and maintain section area head temperature
At 30~35 DEG C, to guarantee that the sulfur trioxide in conversion gas is fully absorbed.
In one example, the acidity distribution of the esterification reaction tower 101 are as follows: SO3Absorber portion (101-1) 10~15%,
Dimethyl ether DME absorbs esterification section (101-2) 3~10%, aging section (101-3) < 1%.Specifically work as SO3Absorber portion (101-1) object
Material acidity is transferred to dimethyl ether DME when reaching 10~12% and absorbs esterification section (101-2)；Material absorbs ester in dimethyl ether DME
Change section (101-2) and absorb dimethyl ether generation esterification, acidity is transferred to aging section (101-3) when being reduced to 3~10%；Always
Change section (101-3) further occurrence esterification, until being transitioned off esterification reaction tower (101) entrance when acidity drops to 1% or less
Degassing tower (102).In the process one can be realized by adjusting the relative discharge size of sulfur trioxide, dimethyl ether and thick dimethyl suflfate
Determine the acidity adjustment of degree.
In one example, the operating pressure of the degassing tower 102 is -0.06~0.1MPa, column bottom temperature 100~120
℃。
In one example, the gaseous mass for returning to three-level esterification reaction tower 101 by 102 tower top of rectifying column forms
For DME:SO3=(7~9): (3~1).
In one example, the operating pressure of the rectifying column 103 is -0.06~-0.1MPa, column bottom temperature 120~160
℃。
In one example, into SO3The group of the conversion gas of absorber portion (101-1) becomes SO3Content is 7~12%.
In one example, the gaseous mass group for returning to three-level esterification reaction tower 101 by 102 tower top of rectifying column becomes
DME:SO3=(7~9): (3~1).
In one example, into the SO of three-level esterification reaction tower 1013Absorptivity >=99.95%.
In one example, the operating pressure of the rectifying column 103 is -0.06~-0.1MPa, column bottom temperature 120~160
℃。
In one example, the SO of the three-level esterification reaction tower 1013Absorber portion (101-1), degassing tower 102, rectifying column
103 be packed tower.
Dimethyl sulfate product purity obtained by the process that dimethyl suflfate according to an embodiment of the present invention continuously synthesizes >
99.5%, acidity < 0.03%.
The invention has the benefit that the process process for preparing dimethyl suflfate is simple, energy consumption is reduced, is reduced investment outlay
Cost, the production technology of serialization have prevented the appearance of the production problem such as run, drip, leak, are also realization large-scale industrial production
It provides safeguard.Gained dimethyl sulfate product is (>99.5%) with high purity, and acidity is low (<0.03%).
Detailed description of the invention
Fig. 1 is the process schematic diagram that dimethyl suflfate continuously synthesizes.
Figure label: 101- three-level esterification reaction tower, 101-1-SO3Absorber portion, 101-2-DME absorb esterification section, 101-
3- aging section, 101-4,101-11- gas distributor, the outlet of 101-5- reaction solution, 101-6- reaction solution entrance, 101-7- reaction
Liquid outlet, 101-8- reaction solution entrance, 101-9 demister, 101-10- liquid distribution trough, 102- degassing tower, 103- rectifying column,
105-1,105-2- reboiler, 106-1,106-2,106-3- condensing heat exchanger.
Fig. 2 is the arrangement of tower grade component and the schematic shapes (front view) in 101-2 sections of areas and 101-3 sections of areas.In 2-1 tower body
Wall, 2-2 fan-shaped component.
Fig. 3 is the arrangement of tower grade component and the schematic shapes (top view) in 101-2 sections of areas and 101-3 sections of areas.3-1 sector structure
Part, 3-2 tower body inner wall.
Specific embodiment
The present invention is further illustrated referring to embodiment and attached drawing, it should be understood that these embodiments are only to use
It is not limitation of the present invention in illustrative explanation.Appoint without departing from the scope of the subject in the invention to what the present invention carried out
What modification is each fallen in the scope of protection of present invention.
Embodiment 1
It is evenly dispersed to filler that thick dimethyl suflfate (25 DEG C of T ≈) enters 101-1 sections of Qu Houjing liquid distribution trough 101-10
Layer, packing layer are filled with ring packing.Pyrolytic conversion gas (SO simultaneously37%, N282.4%, O28.8%, SO21.8%) into
It is flowed up after entering in tower body through gas distributor 101-11 is evenly dispersed.The two inversely contacts, and converts the SO in gas3By sulfuric acid
Dimethyl ester dissolution absorbs, and forms burnt ester；Remaining gas is gone out after demister 101-9 separates entrainment by the gas of tower top
Mouth is discharged into subsequent vent gas treatment workshop section.Because conversion temperature degree is very high and absorption process be it is exothermic, section area passes through cold
Solidifying heat exchanger 106-1 realizes temperature control, is kept for 30 DEG C.Controlling pH is in 9% (based on sulfuric acid content) left and right, when 101-1 sections
Area's coke ester material acidity passes through material outlet 101-5 and material inlet 101-6 when reaching≤9% and is transferred to 101-2 sections of areas.
The bottom inlet in DME from 101-2 sections of areas enters in tower, is uniformly dispersed through 101-4 gas distributor, molten by the burnt ester in section area
Solution absorbs, the SO in part DME and burnt ester3It contacts with each other and esterification occurs and generate dimethyl suflfate, so section area acidity
Decline, when acidity is reduced to 8% by material outlet 101-7 and material inlet 101-8 handling material to 101-3 sections
Area, 101-2 sections of 75 DEG C of areas.Reaction mass into 101-3 sections of areas, which further contacts, occurs esterification, generates dimethyl sulfate
Ester.95 DEG C of temperature of area of section, operating pressure 0.15MPa.When acidity drops to 1% or less, handling material leaves esterification reaction tower
101 enter degassing tower 102.The SO of esterification reaction tower 1013Absorptivity is 99.98%.
In degasification process, reaction solution enters degassing tower 102 by esterification reaction tower 101, and degassing tower belongs to packed tower, is filled with
Ring packing is heated by steam by DME and SO unreacted in dimethyl suflfate reaction solution3It separates, and returns from tower top
The 101-2 section area for returning esterification reaction tower 101, continues to react, and the quality group for the gas isolated becomes DME:SO3=4:1.
The operating pressure of degassing tower 102 be -0.02MPa, 120 DEG C of column bottom temperature.The reaction solution of tower reactor bottom is vaporized through reboiler 105-1
It comes back in tower.Dimethyl suflfate after degassed is produced from tower bottom, and a part is transferred in rectifying column 103 and is depressurized
Rectifying returns to the 101-1 section area of esterification reaction tower 101 after a part of water cooled device 106-2 condensing heat-exchange.
In distillation process, the thick dimethyl sulfate ester articles being transferred into rectifying column 103 reach -0.1MPa, tower in vacuum degree
When kettle temperature degree reaches 120 DEG C, dimethyl suflfate starts heated vaporization, and with the continuation of process, material composition constantly changes in kettle,
Evaporating temperature is gradually increasing, and when rising to 145 DEG C or so, material has steamed substantially, distills maximum temperature less than 160 DEG C.Vaporization
High-purity dimethyl sulfate afterwards is condensed through condensing heat exchanger 106-3, and a part is produced as product, and obtaining purity is 99.9%
Dimethyl sulfate product, acidity 0.01%；A part returns to rectifying column 103 and continues rectifying.The minute quantity that process generates is not coagulated
Exhaust gas removes exhaust gas processing device by the gas outlet of tower top.Tower reactor produces byproduct methyl-hydrogen-sulfate monomethyl-sulfate, and reboiler is arranged in bottom
105-2 vaporizes tower reactor mixture again to return to tower reactor.
Embodiment 2
It is evenly dispersed to filler that thick dimethyl suflfate (25 DEG C of T ≈) enters 101-1 sections of Qu Houjing liquid distribution trough 101-10
Layer, packing layer are filled with ring packing.Pyrolytic conversion gas (SO simultaneously39.6%, N280.1%, O28.8%, SO21.5%)
It is flowed up after in into tower body through gas distributor 101-11 is evenly dispersed.The two inversely contacts, and converts the SO in gas3By sulphur
Dimethyl phthalate dissolution absorbs, and forms burnt ester；Remaining gas passes through the gas of tower top after demister 101-9 separates entrainment
Outlet is discharged into subsequent vent gas treatment workshop section.Because conversion temperature degree is very high and absorption process be it is exothermic, section area passes through
Condensing heat exchanger 106-1 realizes temperature control, is kept for 45 DEG C.Controlling pH works as 101-1 in 12% (based on sulfuric acid content) left and right
Section area coke ester material acidity passes through material outlet 101-5 when reaching≤12% and material inlet 101-6 is transferred to 101-2 sections
Area.The bottom inlet in DME from 101-2 sections of areas enters in tower, is uniformly dispersed through 101-4 gas distributor, by the burnt ester in section area
Dissolution absorbs, the SO in part DME and burnt ester3It contacts with each other and esterification occurs and generate dimethyl suflfate, so section area is sour
Degree declines, and passes through material outlet 101-7 and material inlet 101-8 handling material when acidity is reduced to 10% to 101-3
Section area, 101-2 sections of 80 DEG C of areas.Reaction mass into 101-3 sections of areas, which further contacts, occurs esterification, generates dimethyl sulfate
Ester.95 DEG C of temperature of area of section, operating pressure 0.15MPa.When acidity drops to 1% or less, handling material leaves esterification reaction tower
101 enter degassing tower 102.The SO of esterification reaction tower 1013Absorptivity is 99.95%.
In degasification process, reaction solution enters degassing tower 102 by esterification reaction tower 101, and degassing tower belongs to packed tower, is filled with
Ring packing is heated by steam by DME and SO unreacted in dimethyl suflfate reaction solution3It separates, and returns from tower top
The 101-2 section area for returning esterification reaction tower 101, continues to react, and the quality group for the gas isolated becomes DME:SO3=8:3.
The operating pressure of degassing tower 102 be -0.02MPa, 120 DEG C of column bottom temperature.The reaction solution of tower reactor bottom is vaporized through reboiler 105-1
It comes back in tower.Dimethyl suflfate after degassed is produced from tower bottom, and a part is transferred in rectifying column 103 and is depressurized
Rectifying returns to the 101-1 section area of esterification reaction tower 101 after a part of water cooled device 106-2 condensing heat-exchange.
In distillation process, the thick dimethyl sulfate ester articles being transferred into rectifying column 103 reach -0.1MPa, tower in vacuum degree
When kettle temperature degree reaches 120 DEG C, dimethyl suflfate starts heated vaporization, and with the continuation of process, material composition constantly changes in kettle,
Evaporating temperature is gradually increasing, and when rising to 145 DEG C or so, material has steamed substantially, distills maximum temperature less than 160 DEG C.Vaporization
High-purity dimethyl sulfate afterwards is condensed through condensing heat exchanger 106-3, and a part is produced as product, and obtaining purity is 99.7%
Dimethyl sulfate product, acidity 0.02%；A part returns to rectifying column 103 and continues rectifying.The minute quantity that process generates is not coagulated
Exhaust gas removes exhaust gas processing device by the gas outlet of tower top.Tower reactor produces byproduct methyl-hydrogen-sulfate monomethyl-sulfate, and reboiler is arranged in bottom
105-2 vaporizes tower reactor mixture again to return to tower reactor.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (10)
1. a kind of process of continuous synthesis dimethyl suflfate, it is characterised in that: two kinds of raw material elder generations of sulfur trioxide and dimethyl ether
It is absorbed afterwards in the different section areas of three-level esterification reaction tower by thick dimethyl suflfate, contacts and react generation dimethyl suflfate, by
Degassing and rectifying separation process obtain dimethyl sulfate product and byproduct methyl-hydrogen-sulfate monomethyl-sulfate, and the method includes following mistakes
Journey:
(1) continuous synthetic reaction process: the process occurs in three-level esterification reaction tower (101), and reaction tower (101) is divided into SO3It inhales
Section (101-1), dimethyl ether DME absorption esterification section (101-2), three area Ge Duan of aging section (101-3) are received, thick dimethyl suflfate passes through
Entrance positioned at tower top continuously enters absorber portion (101-1), is dispersed to packing layer through liquid distribution trough (101-10), contains three
The conversion gas of sulfur oxide and dimethyl ether is entered in tower body by being located at the entrance of the bottom absorber portion (101-1), through gas distributor
(101-11) distribution, when it is upwardly through filler laminar flow, and thick dimethyl suflfate is gas-liquid conversed contacts, and converts three in gas
Sulfur oxide is dissolved, absorbs, and forms burnt ester；Burnt ester passes through the outlet (101-5) for being located at tower wall and entrance (101-6) by absorber portion
(101-1) is transferred to dimethyl ether DME and absorbs esterification section (101-2), dimethyl ether DME absorption esterification section (101-2), dimethyl ether
DME enters in tower from the bottom inlet that dimethyl ether DME absorbs esterification section (101-2), disperses through gas distributor (101-4) equal
It is even, the burnt ester dissolution in esterification section (101-2) section area is absorbed by dimethyl ether DME, is absorbed, in part dimethyl ether DME and burnt ester
SO3It contacts with each other and esterification occurs and generate dimethyl suflfate；Dimethyl ether DME absorbs the reaction solution warp of esterification section (101-2)
Outlet (101-7) and entrance (101-8) absorb esterification section (101-2) by dimethyl ether DME and are transferred to aging section (101-3),
Dimethyl ether DME absorbs esterification section (101-2) unreacted material, and in aging section (101-3), further contact generation esterification is raw
At dimethyl suflfate；
(2) degassing and distillation process: contain unreacted raw material in the dimethyl suflfate reaction solution from esterification reaction tower (101)
Dimethyl ether DME and sulfur trioxide SO3, for reaction solution by esterification reaction tower (101) into degassing tower (102), degassing tower passes through steam
Heating, by DME and SO unreacted in dimethyl suflfate reaction solution3It separates, and returns to the diformazan of esterification reaction tower (101)
Ether DME absorb esterification section (101-2), continue to react, it is degassed after dimethyl suflfate a part be transferred to rectifying column
(103) rectification under vacuum is carried out in, and the SO of esterification reaction tower (101) is returned after a part of water cooled device (106-2) condensing heat-exchange3It inhales
It receives section (101-1), the cooling rear portion of the water cooled device of dimethyl suflfate steam (106-3) on rectifying column (103) tower top returns
Tower body continues rectifying, and a part is produced as product, obtains dimethyl sulfate product；Vacuum system fixed gas is from after tower top discharge
Exhaust gas processing device is removed, rectifying tower reactor obtains byproduct methyl-hydrogen-sulfate monomethyl-sulfate,
Dimethyl ether DME absorption esterification section (101-2) of the three-level esterification reaction tower and aging section (101-3) are internally provided with more
Locate tower grade component, is distributed in the tower body inner wall in section area, the fan-shaped structure of tower grade component.
2. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that esterification reaction tower
(101) Temperature Distribution are as follows: SO330~70 DEG C of absorber portion (101-1), dimethyl ether DME absorb esterification section (101-2) 70~85
DEG C, 85~95 DEG C of aging section (101-3), operating pressure is 0.1~0.2MPa.Wherein SO3Absorber portion (101-1) setting condensation is changed
Hot device (106-1) removes partial heat and maintains section area head temperature at 30~35 DEG C, to guarantee the sulfur trioxide quilt in conversion gas
It fully absorbs.
3. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that esterification reaction tower
101 acidity distribution are as follows: SO3Absorber portion (101-1) 10~15%, dimethyl ether DME absorb esterification section (101-2) 3~10%, always
Change section (101-3) < 1%,
Wherein work as SO3Absorber portion (101-1) material acidity is transferred to dimethyl ether DME and absorbs esterification section when reaching 10~12%
(101-2)；Material absorbs esterification section (101-2) and absorb dimethyl ether in dimethyl ether DME occurs esterification, and acidity is reduced to 3~
Aging section (101-3) is transferred to when 10%；Aging section (101-3) further occurrence esterification, until acidity drops to 1% or less
When, esterification reaction tower (101) are transitioned off into degassing tower (102), in the process by adjusting sulfur trioxide, dimethyl ether and thick sulphur
The relative discharge size of dimethyl phthalate realizes acidity adjustment.
4. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that degassing tower (102)
Operating pressure be -0.06~0.1MPa, 100~120 DEG C of column bottom temperature.
5. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that enter SO3Absorber portion
The group of the conversion gas of (101-1) becomes SO3Content is 7~12%.
6. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that by rectifying column
(102) the gaseous mass group that tower top returns to three-level esterification reaction tower (101) becomes DME:SO3=(7~9): (3~1).
7. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that enter three-level and be esterified
The SO of reaction tower (101)3Absorptivity >=99.95%.
8. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that rectifying column (103)
Operating pressure be -0.06~-0.1MPa, 120~160 DEG C of column bottom temperature.
9. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that the three-level esterification
The SO of reaction tower (101)3Absorber portion (101-1), degassing tower (102), rectifying column (103) is packed tower.
10. the process that dimethyl suflfate according to claim 1 continuously synthesizes, which is characterized in that gained sulfuric acid two
Methyl esters product purity>99.5%, acidity<0.03%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910108585.1A CN109748827B (en) | 2019-02-03 | 2019-02-03 | Process for continuous synthesis of dimethyl sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910108585.1A CN109748827B (en) | 2019-02-03 | 2019-02-03 | Process for continuous synthesis of dimethyl sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109748827A true CN109748827A (en) | 2019-05-14 |
| CN109748827B CN109748827B (en) | 2021-09-14 |
Family
ID=66407416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910108585.1A Active CN109748827B (en) | 2019-02-03 | 2019-02-03 | Process for continuous synthesis of dimethyl sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109748827B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028555A (en) * | 2022-07-04 | 2022-09-09 | 武汉青江化工黄冈有限公司 | Diethyl sulfate continuous synthesis process |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105064A (en) * | 1986-08-09 | 1987-04-22 | 山东新华制药厂 | The lower concentration sulphur trioxide is made the method for methyl-sulfate |
| DE4121409A1 (en) * | 1991-06-28 | 1993-01-14 | Bitterfeld Wolfen Chemie | Di:methyl sulphate prodn. from di:methyl ether and sulphur tri:oxide - using safe simple plant connected to combustion plant with flue gas desulphurisation |
| CN1272489A (en) * | 1999-04-30 | 2000-11-08 | 山东淄博新华化工股份有限公司 | Method for extracting dimethyl sulfate by using sulfur as initiation raw material |
| WO2001017937A1 (en) * | 1999-09-09 | 2001-03-15 | Siemens Axiva Gmbh & Co. Kg | Method for producing dimethylether |
| US20070078285A1 (en) * | 2005-09-30 | 2007-04-05 | Battelle Memorial Institute | Dimethyl ether production from methanol and/or syngas |
| CN101654420A (en) * | 2008-08-20 | 2010-02-24 | 湖北富驰化工医药股份有限公司 | Production process for preparing dimethyl sulfate by composite acid through catalytic dehydration |
| CN102249953A (en) * | 2011-05-20 | 2011-11-23 | 山东兴辉化工有限公司 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
| CN103566851A (en) * | 2013-10-30 | 2014-02-12 | 临沂远博化工有限公司 | Dimethyl sulfate esterification reaction tower |
| CN103570590A (en) * | 2013-10-30 | 2014-02-12 | 临沂远博化工有限公司 | Equipment for producing dimethyl sulfate |
| CN203545916U (en) * | 2013-10-30 | 2014-04-16 | 临沂远博化工有限公司 | Equipment for producing dimethyl sulfate |
| CN203540522U (en) * | 2013-10-30 | 2014-04-16 | 临沂远博化工有限公司 | Reaction tower for dimethyl sulfate esterification |
| US9073837B2 (en) * | 2006-12-08 | 2015-07-07 | Centre National De La Recherche Scientifique (C.N.R.S.) | Dehydration of methanol to dimethyl ether using catalysts based on a zeolite supported on silicon carbide |
| CN106699610A (en) * | 2016-12-21 | 2017-05-24 | 武汉青江化工黄冈有限公司 | Process and device for producing dimethyl sulfate with low methyl ether content |
-
2019
- 2019-02-03 CN CN201910108585.1A patent/CN109748827B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105064A (en) * | 1986-08-09 | 1987-04-22 | 山东新华制药厂 | The lower concentration sulphur trioxide is made the method for methyl-sulfate |
| DE4121409A1 (en) * | 1991-06-28 | 1993-01-14 | Bitterfeld Wolfen Chemie | Di:methyl sulphate prodn. from di:methyl ether and sulphur tri:oxide - using safe simple plant connected to combustion plant with flue gas desulphurisation |
| CN1272489A (en) * | 1999-04-30 | 2000-11-08 | 山东淄博新华化工股份有限公司 | Method for extracting dimethyl sulfate by using sulfur as initiation raw material |
| WO2001017937A1 (en) * | 1999-09-09 | 2001-03-15 | Siemens Axiva Gmbh & Co. Kg | Method for producing dimethylether |
| US20070078285A1 (en) * | 2005-09-30 | 2007-04-05 | Battelle Memorial Institute | Dimethyl ether production from methanol and/or syngas |
| US9073837B2 (en) * | 2006-12-08 | 2015-07-07 | Centre National De La Recherche Scientifique (C.N.R.S.) | Dehydration of methanol to dimethyl ether using catalysts based on a zeolite supported on silicon carbide |
| CN101654420A (en) * | 2008-08-20 | 2010-02-24 | 湖北富驰化工医药股份有限公司 | Production process for preparing dimethyl sulfate by composite acid through catalytic dehydration |
| CN102249953A (en) * | 2011-05-20 | 2011-11-23 | 山东兴辉化工有限公司 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
| CN103570590A (en) * | 2013-10-30 | 2014-02-12 | 临沂远博化工有限公司 | Equipment for producing dimethyl sulfate |
| CN203545916U (en) * | 2013-10-30 | 2014-04-16 | 临沂远博化工有限公司 | Equipment for producing dimethyl sulfate |
| CN203540522U (en) * | 2013-10-30 | 2014-04-16 | 临沂远博化工有限公司 | Reaction tower for dimethyl sulfate esterification |
| CN103566851A (en) * | 2013-10-30 | 2014-02-12 | 临沂远博化工有限公司 | Dimethyl sulfate esterification reaction tower |
| CN106699610A (en) * | 2016-12-21 | 2017-05-24 | 武汉青江化工黄冈有限公司 | Process and device for producing dimethyl sulfate with low methyl ether content |
Non-Patent Citations (1)
| Title |
|---|
| 沈家俊: "硫酸二甲酯的生产工艺和环境保护", 《硫酸工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028555A (en) * | 2022-07-04 | 2022-09-09 | 武汉青江化工黄冈有限公司 | Diethyl sulfate continuous synthesis process |
| CN115028555B (en) * | 2022-07-04 | 2023-09-29 | 武汉青江化工黄冈有限公司 | Continuous synthesis process of diethyl sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109748827B (en) | 2021-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101735045B (en) | Method for producing ethyl acetate by using entrainer | |
| CN104030920B (en) | A kind of method of synthesizing fatty acid methyl ester | |
| CN105327518B (en) | The concentration systems and method of a kind of pentanediamine | |
| CN105001072B (en) | Propylene system acrylic acid oxidative absorption system and method | |
| CN104370740B (en) | Compounding acetic isoborneol ester production method | |
| CN109438179A (en) | A kind of reactive distillation prepares the power-economizing method of isopropanol | |
| CN109748827A (en) | The process of continuous synthesis dimethyl suflfate | |
| CN107652322A (en) | Rearranged reaction prepares 2 chloroethyl di(2-ethylhexyl)phosphates（2 chloroethyls）The method of ester | |
| CN110437064A (en) | A kind of differential pressure type energy-saving processing technique of ethyl acetate | |
| CN104860819B (en) | Transformation and heat pump distillation integrated separation butyl acetate and the method and system of n-butanol | |
| CN104193708A (en) | Method and device for separating maleic anhydride from gas phase material flow containing maleic anhydride | |
| CN209098538U (en) | A kind of flue gas recirculation formaldehyde production device | |
| CN201775977U (en) | Treatment device for reaction tail gas in trimellitic acid production | |
| CN105777540A (en) | Energy-saving efficient isopropenyl acetate synthesis method | |
| CN110818563A (en) | Method and device for preparing vinyl acetate through reactive distillation | |
| CN106699610B (en) | The dimethyl suflfate production process and device of low content dimethyl ether | |
| CN216703358U (en) | Methanol vaporizer of silver method formaldehyde production technology | |
| CN105777511B (en) | A kind of energy-efficient acetylacetone,2,4-pentanedione synthesis technique | |
| CN104829452B (en) | Energy-saving production system of ethyl acetate and corresponding energy-saving production technology | |
| CN202447074U (en) | Reactor for ester exchanging | |
| CN210796289U (en) | High-efficient low energy consumption sodium methoxide purification equipment | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN106745066A (en) | Produce, purify the safe technology and system of hydrogen cyanide | |
| CN112250545A (en) | Reaction system for sodium methoxide alkaline production and application method thereof | |
| CN206188684U (en) | Reduce device that propylene carbonylation process central plain material consumed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Jin Hui Inventor after: Tang Qiang Inventor after: Feng Xiuzhen Inventor after: Ren Lijun Inventor after: Zheng Yanyan Inventor before: Jin Hui Inventor before: Tang Qiang Inventor before: Feng Xiuzhen |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Process for continuous synthesis of dimethyl sulfate Effective date of registration: 20211123 Granted publication date: 20210914 Pledgee: Haihua International Financial Leasing Co.,Ltd. Pledgor: SHANDONG CHRE MATERIAL TECHNOLOGY Co.,Ltd.|BEIJING CHEMICAL REACTION ENGINEERING SCIENCE & TECHNOLOGY CO.,LTD. Registration number: Y2021990001119 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |