CN107778149A - The method for preparing polymethoxy dimethyl ether - Google Patents
The method for preparing polymethoxy dimethyl ether Download PDFInfo
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- CN107778149A CN107778149A CN201610727271.6A CN201610727271A CN107778149A CN 107778149 A CN107778149 A CN 107778149A CN 201610727271 A CN201610727271 A CN 201610727271A CN 107778149 A CN107778149 A CN 107778149A
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- dimethyl ether
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
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Abstract
The invention discloses a kind of method for preparing polymethoxy dimethyl ether, and synthetic reaction generation polymethoxy dimethyl ether PODE is directly carried out using dimethyl ether as raw material3~5Or PODE3~8.The present invention is to produce polymethoxy dimethyl ether by raw material, direct catalytic reaction of dimethyl ether, its technical process flow is most short, production process is simple, equipment is simple, reaction raw materials are not aqueous, production process does not also produce water, for improving the reaction speed of this course of reaction, promoting reaction balance to be shifted to generation product direction and can reducing side reaction, energy consumption is low, " three wastes " can reach near-zero release；And its output investment ratio uses existing formaldehyde series of products to reduce by 50% ~ 70% for feed process.
Description
Technical field
The present invention relates to a kind of method for preparing polymethoxy dimethyl ether, belongs to methanol chemistry extension product production technology skill
Art field.
Background technology
The pollution of China's atmospheric environment has govern the sustainable development of Chinese national economy, due to motor vehicle, mainly
It is that diesel automobile exhaust tail gas causes serious haze Wu Ran And to atmospheric environment and people's health is had a strong impact on.Nearly two
Year, statistics represented, PM particulate matters are that the big or middle city atmospheric environment in China produces serious haze in motor-driven fuel-engined vehicle tail gas
One of primary pollution source of pollution, it is the primary pollution sources that the big city such as Beijing atmospheric environment produces serious haze pollution.It is motor-driven
Car (particularly diesel vehicle) exhaust emissions has turned into the important pollution sources of China's air environmental pollution.Haze weather frequently occurs,
How PM2.5, tail gas pollution of motor-driven vehicle are effectively administered, turn into the hot issue that Chinese society all circles seriously pay close attention to.
The development practice of last 100 yearses automobile industry has confirmed, only with the efficiency of combustion for improving motor vehicle and improves gasoline
With the cleannes of diesel oil in itself, not only invest very greatly, and petrol and diesel oil car engine is after continual technology wound of over one hundred year
Newly, it has been difficult to receive positive effect by technological transformation；Domestic and international expert generally acknowledges：Oxygen-containing Tiao is added in the oil He Group divides methyl- tert fourth
Base ether (MTBE) has been achieved with good effect and widely used；It is diesel oil cleaningization development that oxygen-containing component is added in diesel oil
Important and effective direction.
Domestic patent of invention and the technology of the domestic production polymethoxy dimethyl ether promoted are with methanol at present
It is raw material with formaldehyde series product：For example with methanol and metaformaldehyde and be raw material, dimethoxym ethane and metaformaldehyde and be raw material,
It for 85% concentrated formaldehyde and dimethoxym ethane is raw material that dimethoxym ethane and paraformaldehyde, which are raw material or use content,.Such as Chinese patent is public
A kind of method for producing polymethoxy dimethyl ether, publication date 2015-10-14 disclosed in the number of opening 104974025A.
External patent of invention except use methanol and metaformaldehyde and for raw material, dimethoxym ethane and metaformaldehyde and be raw material it
Outside, the side of polymethoxy dimethyl ether is also produced with metaformaldehyde or formaldehyde reaction using dialkyl ether (mainly dimethyl ether)
Method.Such as (China Patent No. is patent disclosed in BASF Aktiengesellschaft:The A of CN 101198576) be using dimethyl ether with
Trioxane（Also referred to as metaformaldehyde）Polymethoxy dimethyl ether is prepared in the presence of acidic（DMMn）Technique.
This method is by dimethyl ether, trioxane（I.e.:Metaformaldehyde）Add in reactor, in the presence of acidic instead
Should, the DMMn cuts for including wherein n=3 and n=4 are obtained by distilling, and unreacted dimethyl ether, trioxane and n<3、
n>4 DMMn is re-circulated into reactor.And a collection of United States Patent (USP) that BP companies declare and authorized（Patent No.:USP
6160186th, 5959156,6160174,6166266,6265528 B1,6360919 B1,6350919 B1,6392102 B1 are total to
Seven）, they all relate to the reaction of dimethyl ether and anhydrous formaldehyde, and (and this anhydrous formaldehyde is using methanol or dimethyl ether as original
Material, through anhydrous formaldehyde made of dehydrogenation ＜ or oxidative dehydrogenation ＞), most representative patented technology is in above-mentioned BP house journals
USP 6160186, title are that " dimethyl ether prepares polymethoxy diformazan with anhydrous formaldehyde catalytic reaction made of dimethyl ether dehydrogenation
Ether ", its technical process are that raw material dimethyl ether is divided into two-way:All the way anhydrous formaldehyde is made by catalytic dehydrogenating reaction（Using
CuZnTiO/Al2O3 catalyst, it is counter answer warm degree Approximately for 600 ~ 700 DEG C, reaction institute calorific requirement be specially the heating furnace that sets supply
Heat）, the anhydrous formaldehyde The of generation, which crosses, to be absorbed formaldehyde using methanol absorber tower, isolates a small amount of on-condensible gas of side reaction generation
(mainly methane, hydrogen, C0, C02), on-condensible gas send heating furnace to be used as supplement fuel；Methanol and anhydrous formaldehyde then with separately
Enter another-catalytic reactor after the mixing of dimethyl ether raw material all the way（Catalyst is ZSM type acidic molecular sieves）Generated after middle reaction poly-
Methoxyl group dimethyl ether etc., through isolating, unreacted dimethyl ether sends reactor cycles utilization back to reaction product, liquid-phase product is sent instead
Answer distillation column reactor and isolate polymethoxy dimethyl ether product.Obviously, it is the two-step method using dimethyl ether as raw material.
In above-mentioned technology, with formaldehyde and series of products (including Jia Shrink aldehyde, metaformaldehyde, paraformaldehyde, concentrated formaldehyde（85%）
Deng) for raw material production method existing for subject matter be：
1st, any two raw material in above-mentioned raw materials is selected to match, except metaformaldehyde is anhydrous, although its not aqueous price is too high, skill
Art economic evaluation is difficult to outside receiving, and is difficult to solve the problems, such as aqueous (not only to influence reaction speed when aqueous in raw material, to anti-
It is unfavorable to line of production transfer to balance, and causes side reaction increase, once through yield to reduce the increase of 30% ~ 50%, objectionable impurities
And purify load and require improve, force flow is more complicated, flow is longer, energy consumption increase, investment increase).
2nd, it is total to see, when formaldehyde series of products be raw material, technological process is long, process complexity, equipment are more, high energy consumption, " three
It is useless " toxicity that is more, taking up an area formaldehyde raw material in more, production is larger, investment is higher, cost is higher.
It is above-mentioned with the patented technology of BASF AG and BP companies the problem of be：
1st, it is raw material that although BASF AG, which employs dimethyl ether and metaformaldehyde, has reached substantially anhydrous requirement (BASF
Company require be it is aqueous≤1%), but metaformaldehyde too expensive (about 1.2 ~ 1.6 ten thousand yuan/ton of price), technological economics evaluation are not
Feasible!As used other formaldehyde series raw materials, then aforementioned technical drawbacks are absorbed in again.
2nd, the essence of the patent of BP companies is still the two-step method for using dimethyl ether with formaldehyde for raw material：Its formaldehyde is by first
The anhydrous formaldehyde of alcohol or dimethyl ether by dehydrogenation (or oxidative dehydrogenation) reaction generation；Its advantage is can to reach substantially free of water
It is required that, can receive in Technological Economy；But it still has that flow is very long, equipment is a lot, process is complicated, high energy consumption, " three
It is useless " it is more, take up an area and be still related to the big formaldehyde raw material production of toxicity in more, production, invest the shortcomings that higher, cost is higher.
The content of the invention
It is an object of the invention to overcome above mentioned problem existing for prior art, there is provided one kind prepares polymethoxy dimethyl ether
Method.The present invention is to produce polymethoxy dimethyl ether by raw material, direct catalytic reaction of dimethyl ether, and its technical process flow is most
It is short, production process is simple, equipment is simple, reaction raw materials are not aqueous, and production process does not also produce water, reacted for improving this
The reaction speed of journey, promote reaction balance to be shifted to generation product direction and side reaction can be reduced, energy consumption is low, " three wastes " can
Reach near-zero release；And its output investment ratio uses existing formaldehyde series of products to reduce by 50% ~ 70% for the method for raw material.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of method for preparing polymethoxy dimethyl ether, it is characterised in that:Synthetic reaction life is directly carried out by raw material of dimethyl ether
Into polymethoxy dimethyl ether PODE3~5Or PODE3~8。
It is described that synthetic reaction is carried out in fixed bed catalytic reactor by raw material of dimethyl ether, fixed bed catalytic reactor
Internal downward from top feed dimethyl ether import, upper air side is filled with catalyst A, bottom loading catalyst B.
The fixed bed catalytic reactor top is shell heat exchange isotherm formula structure, and catalyst A is seated in pipe, between shell
Water flowing heat exchange removes partial reaction heat；The bottom of reactor is adiabatic reaction catalyst layer, and its structure is drum-shaped, catalyst B
Uniformly stow, water cooling coil pipe is provided with before reaction mass enters adiabatic reaction catalyst layer or the regulation and control of tubulation component enter absolutely
The temperature of thermal response catalyst layer.
The process conditions of synthetic reaction are carried out in the fixed bed catalytic reactor is：Reaction pressure is 0.05 ~ 1.5MPa,
Reaction temperature is 70 DEG C ~ 450 DEG C, and wherein epimere catalyst temperature is 150 DEG C ~ 450 DEG C, and lower section catalyst temperature is 70 DEG C ~ 150
DEG C, gas of dimethyl ether stereometer air speed is 800 ~ 15000hr-1；The addition of oxygen is gas of dimethyl ether stereometer dosage
Volume proportion between 0.5% ~ 25%, catalyst A and catalyst B loadings is 1：0.5~2.5.
The catalyst A is by Al2O3、CaO、MgO、La2O3、Ce2O3, TeO, SeO, SnO, CuO, ZnO, NiO be raw material,
Raw material is sequentially 20 ~ 70 by number proportion scale: 2~25 : 15~55 : 0.5~5.5 : 0.2~4.5 : 3~6 : 5~10
: 1.5~12 : 1~3 : 2~5 : 3~6；It is molten at least by being configured to nitrate solution from more than 5 kinds raw materials in above-mentioned raw materials
Liquid concentration is in mass 10% ~ 25%, through K2CO3Solution neutralization reaction, the pH value 7.0 ~ 7.05 after neutralization reaction, filters and goes
Ion water washing, isolated filter cake, filter cake is after 120 DEG C are dried 2 ~ 3 hours, 350 DEG C ~ 550 DEG C and are calcined 2 ~ 3 hours, then mixes
It is even, levigate to add the graphite and the deionized water of material quality 7 ~ 10% of material quality 1 ~ 3% to 80 ~ 120 mesh, mix, be granulated, pressure
Type, which is made, turns into Φ 5x5x1.5 or Φ 6x6x2 (the high x internal diameters of external diameter x) mm Raschig ring.
The catalyst B is used from the cationic ion-exchange resin of moderate acid, solid acid catalysts or ZSM-5 types
One kind is selected in molecular sieve, using manufactured catalyst behind Si/Al ratio >=200 that modified regulation molecular sieve is needed during molecular sieve.
The fixed bed catalytic reactor is one, or for two, and during using two reactors, two fixed beds are urged
Change reactor series winding operation：First reactor is shell heat exchange isotherm formula structure or water cooling plate-type heat exchange structure or water cooling
Snake tube group type or shell and tube heat exchange structure, second fixed bed catalytic reactor are using the heat-insulating for uniformly stowing catalyst B
Bed structure.
The reaction product passes through adsorption deacidification tower adsorbing and removing organic acid, adsorption deacidification tower at least two, wherein one
Operationally, another is then in regeneration stage to individual adsorption tower；Solid base adsorbent is filled with adsorption deacidification tower.Adsorption deacidification
It is to use temp.-changing adsorption technology, adsorption deacidification process is carried out in normal temperature, and adsorbent reactivation desorption process enters at 100 DEG C ~ 300 DEG C
OK.
The solid base adsorbent is the absorption of resin anion (R.A.), solid super base adsorbent or load-type solid
Agent, its carrier are activated carbon, molecular sieve or Al2O3。
The reaction product is by conventional two tower rectifying separation, and first rectifying column is compression rectification tower, Second distillation column
It is atmospheric distillation tower, n >=5 or >=6 material are circulated back in low boiling material and DMMn that unreacted and reaction generates
Fixed bed catalytic reactor utilizes as raw material.
, can be by fixed bed adiabatic catalytic reaction therein when the fixed bed catalytic reactor is divided into two reactors
Device is integrally run with the coupling of separated tower as the mode of catalyzed reaction distillation tower.
Using the advantage of the invention is that：
First, technical process flow of the invention is most short, production process is simple, equipment is simple, and reaction raw materials are not aqueous, production process
Water, the reaction speed to improving this course of reaction and favourable to the movement of generation product direction to reaction balance are not produced yet,
Energy consumption is low, " three wastes " and can reach near-zero release, take up an area can reduce more than 60%, that investment can reduce by 50% ~ 70%, cost is substantially low.
2nd, the present invention generates water-free product, is balanced to synthesising reacting speed, to reaction, to reducing side reaction（Reduce
The objectionable impurities such as formic acid）Favourable, product needs not move through dewater treatment and can reach aqueous≤0.1% quality requirement.
3rd, after using the present invention, DMM3+ conversion per pass yield can improve 10 percentage points（Improve about 35 ~ 40%）,
There is significant effect to reducing investment, reduction energy consumption, reduction material consumption, reduction pollution and CO2 discharges, reducing cost.
Brief description of the drawings
Fig. 1 is combined type fixed bed catalytic reactor structural representation of the present invention；
Fig. 2 uses two fixed bed catalytic reactor process flow diagrams for the present invention；
Fig. 3 uses a fixed bed catalytic reactor process flow diagram for the present invention；
Fig. 4 is integrally formed catalytic reaction for the present invention using by second fixed bed catalytic reactor and the coupling of separated tower
The process flow diagram of rectifying column.
In figure mark for：1st, material inlet mixed distribution device, 2, gas-liquid distributor, 3, upper perforated plate, 4, isothermal reaction section, 5,
Reaction tube, 6, catalyst A, 7, lower perforated plate, 8, water cooling coil pack, 9, circular response material inlet distributor, 10, catalyst B,
11st, flame-proof sphere filler, 12, reacting rear material manifold, a, gas material import, b, liquid material import, c, manhole, d, isothermal
Section water inlet, e, isothermal section water out, f, cooling coil water inlet, g, cooling coil water out, h, circular response material inlet,
I, reacting product outlet.
Embodiment
Embodiment 1
A kind of method for preparing polymethoxy dimethyl ether, synthetic reaction generation polymethoxy two is directly carried out using dimethyl ether as raw material
Methyl ether PODE3~5Or PODE3~8。
Further illustrate, directly carry out synthetic reaction by raw material of dimethyl ether, reaction product takes off by conventional absorption
After micro organic acid, the two tower rectifying by routine, which separate, is made polymethoxy dimethyl ether PODE3~5Or PODE3~8.Mainly
Reaction is as follows：Oxygen addition is the 0.5% ~ 25% of dimethyl ether gaseous feed amount.
CH3OCH3 + 1/2O2 2CH2O + H2
CH3OCH3 + n CH2OCH3O(CH2O)nCH3
It is described that synthetic reaction, the inside of fixed bed catalytic reactor are carried out in fixed bed catalytic reactor by raw material of dimethyl ether
Downward from top feed dimethyl ether import, upper air side is filled with catalyst A, bottom loading catalyst B.
The structure of fixed bed catalytic reactor is shown in accompanying drawing 1, and its top is shell heat exchange isotherm formula structure, and catalyst A is filled
Fill out in pipe, water flowing heat exchange removal reaction heat between shell；The bottom of reactor is adiabatic reaction catalyst layer, and its structure is drum
Shape, catalyst B are uniformly stowed, and water cooling coil pipe or row are provided with before reaction mass enters adiabatic reaction catalyst layer
Temperature of the tube assembly regulation and control into adiabatic reaction catalyst layer.
The process conditions of synthetic reaction are carried out in the fixed bed catalytic reactor is：Reaction pressure is 0.05 ~ 1.5MPa,
Reaction temperature is 70 DEG C ~ 450 DEG C, and wherein epimere catalyst temperature is 150 DEG C ~ 450 DEG C, and lower section catalyst temperature is 70 DEG C ~ 150
DEG C, dimethyl ether air speed is 800 ~ 15000hr-1（Gas volume %）；The addition of oxygen is the 0.5% ~ 25% of dimethyl ether dosage（Gas
Body volume %）, the volume proportion between catalyst A and catalyst B loadings is 1：0.5~2.5.
The catalyst A is by Al2O3、CaO、MgO、La2O3、Ce2O3, TeO, SeO, SnO, CuO, ZnO, NiO be raw material,
Raw material is sequentially 20 ~ 70 by number proportion scale: 2~25 : 15~55 : 0.5~5.5 : 0.2~4.5 : 3~6 : 5~10
: 1.5~12 : 1~3 : 2~5 : 3~6；It is at least molten by being configured to nitrate from more than 5 kinds raw materials in above-mentioned 11 kinds of raw materials
Liquid, solution concentration is in mass 10% ~ 25%, through K2CO3Solution neutralization reaction, the pH value 7.0 ~ 7.05 after neutralization reaction, mistake
Filter and deionized water washing, isolated filter cake, filter cake are dried 2 ~ 3 hours, 350 DEG C ~ 550 DEG C through 120 DEG C and are calcined 2 ~ 3 hours
Afterwards, then mix, be levigate to 80 ~ 120 mesh, adding the graphite and the deionized water of material quality 7 ~ 10% of material quality 1 ~ 3%, mix,
It is granulated, the compressing Raschig ring as Φ 5x5x1.5 or Φ 6x6x2 (the high x internal diameters of external diameter x) mm.
The catalyst B is used from the cationic ion-exchange resin of moderate acid, solid acid catalysts or ZSM-5 types
A kind of, manufactured catalyst behind Si/Al ratio >=200 of modified regulation molecular sieve is selected in molecular sieve.
The reaction product passes through adsorption deacidification tower adsorbing and removing organic acid, adsorption deacidification tower at least two, wherein one
Operationally, another is then in regeneration stage to individual adsorption tower；Solid base adsorbent is filled with adsorption deacidification tower.Absorption is de-
Acid is to use temp.-changing adsorption technology, and adsorption deacidification process is carried out in normal temperature, and adsorbent reactivation desorption process is 100 DEG C ~ 300
DEG C carry out.
The solid base adsorbent is the absorption of resin anion (R.A.), solid super base adsorbent or load-type solid
Agent, its carrier are activated carbon, molecular sieve or Al2O3。
The reaction product is by conventional two tower rectifying separation, and first rectifying column is compression rectification tower, Second distillation column
It is atmospheric distillation tower, unreacted and reaction generation low boiling material（The low boiling materials such as dimethyl ether, formaldehyde, methyl formate）
Fixed bed catalytic reactor is circulated back to n >=5 in DMMn or >=6 material to utilize as raw material.First rectifying column is to add
Rectifying column is pressed, operating pressure is 0.40 ~ 1.0MPa, tower top distillates light fraction dimethoxym ethane, tower middle part distillates unreacted formaldehyde,
Methanol, PODE2Send fixed bed catalytic reactor back to and be used as feedstock circulation；The bottomsstream is sent to the rectifying column of the mat woven of fine bamboo strips two；Second rectifying
Tower is atmospheric distillation tower, and operating pressure is 0.01 ~ 0.40MPa；The bottomsstream of Second distillation column is >=PODE5Or >=
PODE6Mixture, send back to fixed bed catalytic reactor recycling；The overhead PODE of Second distillation column3~4Or
PODE3~5It is polymethoxy dimethyl ether product.
Embodiment 2
The present embodiment is essentially identical with above-described embodiment, and the main distinction is as follows：
Compound fixed bed catalytic reactor is anti-using two operations of fixed bed catalytic reactor series winding, two fixed-bed catalytics are divided into
Answer and distinguish loading catalyst A and catalyst B in device in order；Now, first fixed bed catalytic reactor should be shell heat exchange
Isotherm formula structure（Water cooling plate-type heat-exchange or water cooling snake tube group type heat exchange structure can also be used）；Second fixed bed catalyst
Device is then using the heat-insulating bed structure for uniformly stowing catalyst B.Process flow diagram is shown in Fig. 2.
When the compound fixed bed catalytic reactor is divided into two reactors, it can use second fixed bed is exhausted
Heat catalysis device is integrally formed catalytic rectifying column with the coupling of separated tower.The tower bottom of catalytic rectifying column
Material is distillated after adsorption deacidification, is sent to atmospheric distillation tower, the bottomsstream of atmospheric distillation tower is >=PODE5Or >=
PODE6Mixture, send catalytic rectifying column back to and recycle；The overhead PODE of atmospheric distillation tower3~4Or
PODE3~5It is polymethoxy dimethyl ether production finished product.Process flow diagram is shown in Fig. 4.
Embodiment 3
The present embodiment provide it is a kind of using dimethyl ether as raw material, using the compound fixed bed reaction for being filled with catalyst A and catalyst B
Device（Its structure is shown in accompanying drawing 1）The method for preparing polymethoxy dimethyl ether, technical process are shown in accompanying drawing 3, and its reaction condition is as follows：
Top loading catalyst A, the bottom loading catalyst B, A of compound fixed bed reactors：B==1：1.8th, catalyst amount：A
It it is 64 milliliters for 36 milliliters, B.
By catalyst A loadings, it is desirable to the air speed of dimethyl ether（Gaseous state）For 3000h-1, i.e. 0.5L/min, it is desirable to which oxygen enters
Material tolerance is 0.05L/min.
Reaction pressure is 0.5MPa, catalyst layer reaction temperature：360 DEG C of top, 120 DEG C of bottom.
Feed intake 30 minutes, reaction pressure, reaction temperature reach above-mentioned requirements, and dimethyl ether air speed (aerometer) reaches
1000h-1When start to add oxygen in charge volume ratio, gradually step up dimethyl ether air speed, and by ratio requirement, accordingly carry
High supplying oxygen, altogether by 1.5 hours, dimethyl ether gaseous state air speed reaches ~ 3000h-1[5.0L（Gaseous state）/ min], oxygen adds
Dosage is the 10% of dimethyl ether（0.5L/min）, into stable operation.During stable operation, reactor outlet product analysis result is shown in
Table 1.
It is known that from the analyze data of table 1：Polymethoxy dimethyl ether is produced using the art of this patent in embodiment 3
When, the conversion per pass of dimethyl ether reaches 85.35%； PODE2+The selectivity of target product reaches 66.09%, PODE3+Target
Product once through yield reaches 46.31%, compared with existing formaldehyde method once through yield, PODE3+Product once through yield can improve
35% ~ 46%.
The service condition and tables of data of the examples of implementation of table 1
Embodiment 4
The present embodiment provide it is a kind of using dimethyl ether as raw material, using the compound fixed bed reaction for being filled with catalyst A and catalyst B
Device（Its structure is shown in accompanying drawing 1）The method for preparing polymethoxy dimethyl ether, technical process are shown in accompanying drawing 3, and its reaction condition is as follows：
Top loading catalyst A, the bottom loading catalyst B, A of compound fixed bed reactors：B==1：1.2nd, catalyst amount：
A is 45 milliliters, B is 54 milliliters.
By catalyst A loadings, it is desirable to the air speed of dimethyl ether（Gaseous state）For 4000h-1, i.e. 6.7L/min, it is desirable to which oxygen enters
Material tolerance is 0.54L/min.
Reaction pressure is 0.7MPa, reaction temperature：360 DEG C of top, 120 DEG C of bottom.
Feed intake 30 minutes, reaction pressure, reaction temperature reach above-mentioned requirements, and dimethyl ether air speed (aerometer) reaches
1000h-1When start to add oxygen in charge volume ratio, gradually step up dimethyl ether air speed, and by ratio requirement, accordingly carry
High supplying oxygen, altogether by 1.5 hours, dimethyl ether gaseous state air speed reaches ~ 4000h-1[0.67L（Gaseous state）/ min], oxygen
Addition is the 8% of dimethyl ether（0.054L/min）, into stable operation.During stable operation, reactor outlet product analysis knot
Fruit is shown in Table 1.
It can be seen that from the analyze data of table 1:Polymethoxy dimethyl ether is produced using the art of this patent in example 4
When, the conversion per pass of dimethyl ether reaches 85.10%； PODE2+The selectivity of target product reaches 64.53%, PODE3+Target
Product once through yield reaches 44.19%, compared with existing formaldehyde method once through yield, PODE3+Target product once through yield improves
32% ~ 43%.
Embodiment 5
The present embodiment combination accompanying drawing 1 illustrates to the fixed bed catalytic reactor in the present invention.
As illustrated, as illustrated, a kind of be used to prepare the combined type fixed bed catalytic reactor of polymethoxy dimethyl ether,
Combined type fixed bed catalytic reactor top is shell heat exchange isotherm formula structure, is used to fill in the pipe of shell heat exchange isotherm formula structure
Catalyst is filled out, bottom is the conversion zone for stowing adiabatic reaction catalyst, for example, top loading catalyst A, bottom, which stows, urges
Agent B.
Material inlet mixed distribution device 1, material inlet mixing are provided with the top of the combined type fixed bed catalytic reactor
Gas material import a and liquid material import b are provided with distributor 1, the lower section of material inlet mixed distribution device 1 is provided with gas-liquid
Distributor 2.
The shell heat exchange isotherm formula structure is shell-and-tube heat exchanger, and catalysis is loaded in the reaction tube 5 of shell-and-tube heat exchanger
Agent, water flowing between shell, isothermal section water inlet d and isothermal section water out e is provided with the isothermal reaction section 4 of shell-and-tube heat exchanger.
Gas-liquid distributor 2 is located at the top of upper perforated plate 3 of shell-and-tube heat exchanger.
It is provided between the lower perforated plate 7 of the shell-and-tube heat exchanger and the conversion zone for stowing adiabatic reaction catalyst for adjusting
Water cooling coil pack 8 or tubulation component that reaction mass enters adiabatic reaction catalyst layer temperature are controlled, as illustrated, water cooling coil pipe
Cooling coil water inlet f and cooling coil water out g are provided with component.
The adiabatic reaction catalyst homogeneous reactor is mounted in adiabatic reaction catalyst layer.
Circular response material inlet pipe is provided between the water cooling coil pipe or tubulation component and adiabatic reaction catalyst layer
Road and circular response material inlet distributor 9, circular response material inlet distributor 9 are connected with circular response material inlet h, followed
The lower section of ring reacting material inlet distributor 9 is provided with gas-liquid distributor 2.
The combined type fixed bed catalytic reactor bottom is provided with reacting rear material manifold 12, and reacting rear material collects
Device 12 connects with the reacting product outlet i on combined type fixed bed catalytic reactor, and reacting rear material manifold 12 is arranged on multiple
Box-like fixed bed catalytic reactor bottom and positioned at for support catalyst layer flame-proof sphere filler 11 in.
Multiple through holes passed through for reacting rear material are evenly arranged with the reacting rear material manifold 12.
Combined type fixed bed catalytic reactor top, middle part and the bottom are provided with manhole c.
The combined type fixed bed catalytic reactor is a combined reactor or is provided separately as two reactors, is adopted
During with setting two fixed bed catalytic reactors, two fixed bed catalytic reactor series winding operations：First reactor is shell
Heat exchange isotherm formula structure or water cooling plate-type heat exchange structure or water cooling snake tube group type or shell and tube heat exchange structure, second fixed bed are urged
Change reactor is heat-insulating bed structure.
When the fixed bed catalytic reactor is divided into two reactors, fixed bed adiabatic therein can also be catalyzed anti-
Answer device to be coupled with separated tower integrally to run as the mode of catalyzed reaction distillation tower.
Claims (7)
- A kind of 1. method for preparing polymethoxy dimethyl ether, it is characterised in that:Synthetic reaction is directly carried out by raw material of dimethyl ether Generate polymethoxy dimethyl ether PODE3~5Or PODE3~8。
- 2. the method according to claim 1 for preparing polymethoxy dimethyl ether, it is characterised in that：It is described using dimethyl ether as original Material carries out synthetic reaction in fixed bed catalytic reactor, and the inside of fixed bed catalytic reactor is from top feed dimethyl ether import Downwards, upper air side is filled with catalyst A, bottom loading catalyst B.
- 3. the method according to claim 2 for preparing polymethoxy dimethyl ether, it is characterised in that：The fixed-bed catalytic is anti- It is shell heat exchange isotherm formula structure to answer device top, and catalyst A is seated in pipe, water flowing heat exchange removal partial reaction heat between shell； The bottom of reactor is adiabatic reaction catalyst layer, and its structure is drum-shaped, and catalyst B is uniformly stowed, and is entered in reaction mass Water cooling coil pipe or the regulation and control of tubulation component are provided with before adiabatic reaction catalyst layer into the temperature of adiabatic reaction catalyst layer.
- 4. the method according to claim 3 for preparing polymethoxy dimethyl ether, it is characterised in that：The fixed-bed catalytic is anti- Answering the process conditions that synthetic reaction is carried out in device is：Reaction pressure is 0.05 ~ 1.5MPa, and reaction temperature is 70 DEG C ~ 450 DEG C, its Middle epimere catalyst temperature is 150 DEG C ~ 450 DEG C, and lower section catalyst temperature is 70 DEG C ~ 150 DEG C, gas of dimethyl ether stereometer air speed For 800 ~ 15000hr-1；The addition of oxygen is the 0.5% ~ 25% of gas of dimethyl ether stereometer dosage, catalyst A and catalyst B Volume proportion between loadings is 1：0.5~2.5.
- 5. according to the method for preparing polymethoxy dimethyl ether described in claim 2,3 or 4, it is characterised in that：The catalyst A By Al2O3、CaO、MgO、La2O3、Ce2O3, TeO, SeO, SnO, CuO, ZnO, NiO be raw material, raw material presses number proportion scale It is sequentially 20 ~ 70: 2~25 : 15~55 : 0.5~5.5 : 0.2~4.5 : 3~6 : 5~10 : 1.5~12 : 1~3 : 2~5 : 3~6；At least by being configured to nitrate solution from more than 5 kinds raw materials in above-mentioned raw materials, solution concentration is in mass 10% ~ 25%, through K2CO3Solution neutralization reaction, the pH value 7.0 ~ 7.05 after neutralization reaction, filtering and deionized water washing, separation Filter cake is obtained, filter cake is after 120 DEG C are dried 2 ~ 3 hours, 350 DEG C ~ 550 DEG C and are calcined 2 ~ 3 hours, then mixes, be levigate to 80 ~ 120 Mesh, the graphite and the deionized water of material quality 7 ~ 10% of material quality 1 ~ 3% are added, mix, be granulated, compressing Raschig ring.
- 6. the method according to claim 5 for preparing polymethoxy dimethyl ether, it is characterised in that：The catalyst B is to adopt It is a kind of with being selected from the cationic ion-exchange resin, solid acid catalysts or type ZSM 5 molecular sieve of moderate acid, using point Manufactured catalyst behind Si/Al ratio >=200 of the modified regulation molecular sieve of need during son sieve.
- 7. the method according to claim 6 for preparing polymethoxy dimethyl ether, it is characterised in that：The fixed-bed catalytic is anti- It is one to answer device, or for two, during using two reactors, by two fixed bed catalytic reactors series winding operations：First Reactor is shell heat exchange isotherm formula structure or water cooling plate-type heat exchange structure or water cooling snake tube group type or shell and tube heat exchange knot Structure, second fixed bed catalytic reactor are using the heat-insulating bed structure for uniformly stowing catalyst B.
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| CN113087602A (en) * | 2020-01-09 | 2021-07-09 | 中国石油化工股份有限公司 | Production and refining method of polymethoxy dimethyl ether |
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