CN113087603B - Production system and production method of polymethoxy dimethyl ether - Google Patents
Production system and production method of polymethoxy dimethyl ether Download PDFInfo
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- CN113087603B CN113087603B CN202010021462.7A CN202010021462A CN113087603B CN 113087603 B CN113087603 B CN 113087603B CN 202010021462 A CN202010021462 A CN 202010021462A CN 113087603 B CN113087603 B CN 113087603B
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Abstract
The invention relates to a polyoxymethylene dimethyl ethers production system, including: a reactor; a filter connected to the reactor; the reaction liquid intermediate tank is connected with the filter; and an anion resin neutralization tank connected with the reaction liquid intermediate tank. By improving the production system, the problems of raw material selection, long reaction time, difficult reaction operation, low conversion rate of paraformaldehyde and low effective components in reaction products in the production process of polymethoxy dimethyl ether in the prior art are mainly solved.
Description
Technical Field
The invention relates to the field of petrochemical industry, and particularly relates to a polymethoxy dimethyl ether production system and a polymethoxy dimethyl ether production method.
Background
Polyoxymethylene dimethyl ethers (PODE or DMMn) is a new clean oil additive which is very much concerned in recent years and can improve diesel combustion, increase cetane number and reduce carbon dioxide and NO x And (5) discharging. Polyoxymethylene dimethyl ethers [ CH ] suitable as diesel additives 3 (OCH 2 ) n OCH 3 ]The value of n is more than or equal to 3 and less than or equal to 8, wherein n = 3-4 is the best. Oligomers with n =2 and compounds with n =1 (i.e. methylal), are unsuitable as diesel additives due to their low boiling and flash points; n is a radical of an alkyl radical>The oligomer of 8 is easily crystallized at low temperature and is not suitable as a diesel fuel additive. Only the oligomer with n = 3-4 has a boiling point and a flash point which are equivalent to those of a typical diesel oil mixture, has the properties which are very close to those of diesel oil, has higher oxygen content (45-49%), has a cetane number of 70-90 which is 55-60 higher than that of the conventional common diesel oil, and is a more suitable diesel oil additive.
The synthesis technology of PODE in the world is mainly divided according to the source of the synthesis raw material. Methanol and formaldehyde are the cheapest raw materials, and trioxymethylene, paraformaldehyde and methylal are products produced by further processing formaldehyde, so the price is relatively high. However, formaldehyde is generally present in the form of an aqueous solution, contains a large amount of water, and product separation may be difficult, and in some reactions, the presence of a large amount of water may also inhibit the reaction due to the equilibrium of the reaction. Since polyoxymethylene dimethyl ethers have great application values in the field of diesel additives, many companies and research institutes have been studying practical industrial production technologies for a long time.
US patent US6392102 describes the preparation of pomme by reaction using a stream comprising methanol and formaldehyde obtained by oxidation of dimethyl ether in the presence of an acidic catalyst, with removal of the reactants in a catalytic distillation column. This gave a mixture of methylal, methanol, water and pomme. The process of US6392102 produces formaldehyde by oxidation of dimethyl ether, although the water content is reduced to some extent (> 60% formaldehyde concentration), but the whole process is complicated, including reactive distillation, multiple heterogeneous reactors, distillation columns, absorption columns and spray columns, which requires high development and investment costs, and maintenance costs during operation. In addition, the dimethyl ether is used for replacing methanol to produce formaldehyde, and the cost of raw materials is relatively high.
BP company has done a lot of work on the study of polyoxymethylene dimethyl ethers. They disclose in patents US2002007089 and US 6160186 processes for synthesizing polymethoxy dimethyl ether by respectively selecting methanol, formaldehyde, dimethyl ether and methylal as raw materials.
The first process of the process, namely methanol gas phase catalytic oxidation to prepare formaldehyde, selects a catalyst containing copper, zinc and one element of sulfur, smashing and tellurium as an active component, carries out gas phase dehydrogenation on methanol at high temperature to obtain a mixed gas of formaldehyde, methanol, hydrogen and carbon monoxide, further cools the mixed gas to mainly concentrate the methanol, collects the formaldehyde, and separates a liquid phase part containing the formaldehyde from a gas phase part of the mixed gas of the hydrogen and the carbon monoxide. The feed for the second process of the process comprises methanol and formaldehydeAnd a soluble condensation accelerating component capable of activating the heterogeneous acid catalyst, wherein methanol and formaldehyde react in a catalytic rectifying tower in the presence of the heterogeneous acid catalyst to obtain methylal and polymethoxy dimethyl ether with higher polymerization degree, the methylal and the polymethoxy dimethyl ether are separated, and further, the product is subjected to anion exchange resin to obtain an acid-free product which can be directly mixed into diesel oil, and the acid-free product can also be continuously fractionated, namely, a higher-quality diesel oil adding component is obtained by a distillation method. The acidic catalyst for preparing methylal and polymethoxy dimethyl ether by condensing methanol and formaldehyde at least comprises one of bentonite, montmorillonite, cation exchange resin or sulfonated fluoroolefin resin derivative, preferably sulfonated tetrafluoroethylene resin derivative. The most preferred acidic catalyst is at least one cation exchange resin consisting of styrene-divinylbenzene copolymer, acrylic acid-divinylbenzene copolymer and methacrylic acid-divinylbenzene copolymer. The process synthesizes polymethoxy dimethyl ether by using cheap and easily available raw materials through a heterogeneous catalysis method, however, the yield is still low, and PODE 3-7 Not more than 24.0%. Great efforts are still needed to further improve the yield and realize industrialization.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a polyoxymethylene dimethyl ether production system and a polyoxymethylene dimethyl ether production method, which mainly solve the problems of raw material selection, long reaction time, difficult reaction operation, low paraformaldehyde conversion rate and low effective components in reaction products in the production process of polyoxymethylene dimethyl ether in the prior art by improving the production process. The production method provided by the invention can be used for actually producing polymethoxy dimethyl ether industrially, and has the characteristics of simple operation, controllable reaction time, high target component and specific industrial application.
The invention provides a polyoxymethylene dimethyl ethers production system on one hand, including:
a reactor;
a filter connected to the reactor;
the reaction liquid intermediate tank is connected with the filter; and
and the anion resin neutralization tank is connected with the reaction liquid intermediate tank.
According to the invention, the polymethoxy dimethyl ether production system further comprises a reaction liquid collecting tank connected with the anion resin neutralization tank.
According to the present invention, preferably, the reactor is a stirred tank reactor having heat tracing and heat removing functions, such as a jacketed tank-type stirred reactor.
The inventor of the present application found that compared with the conventional reactor (such as the stainless steel reactor with inner liner used in patent CN 106278835A), the use of the jacketed kettle type stirring reactor is beneficial to the thorough mixing of reactants, and the control of the temperature in the reactor, so as to make the temperature distribution uniform. In addition, the arrangement of the reaction liquid intermediate tank reduces or even avoids the corrosion of equipment by the reaction liquid and the polymerization of by-products in the reaction liquid under acidic conditions.
According to the present invention, the anion resin neutralization tank is filled with at least one of a solid base catalyst, an anion exchange resin catalyst and a basic molecular sieve. The inventor of the application finds that the arrangement of the anion resin neutralization tank is beneficial to preventing the reaction liquid from corroding equipment and preventing byproducts in the reaction liquid from polymerizing under the acidic condition.
In a preferred embodiment of the present invention, the discharge opening of the jacketed stirred-tank reactor is located at 40% to 80% of the height of the jacketed stirred-tank reactor.
In a preferred embodiment of the invention, the outlet of the reactor is located at 50% to 70% of the height of the reactor.
In a preferred embodiment of the invention, the outlet of the reactor is located at 60% to 70% of the height of the reactor.
According to the invention, the discharge hole of the reactor is arranged at 50-70% of the height of the reactor, especially 60-70% of the height of the reactor, so that the catalyst entrained in the product flow can be primarily filtered, and the content of the catalyst in the product flow can be reduced.
In a preferred embodiment of the present invention, the height of the head difference between the reactor and the reaction liquid intermediate tank is not less than 1.5m.
In a preferred embodiment of the present invention, the height of the head difference between the reactor and the reaction liquid intermediate tank is not less than 2.0m.
According to the invention, when the height of the potential difference between the reactor and the reaction liquid intermediate tank is not less than 1.5m, especially not less than 2.0m, the transportation of the material flow can be realized by utilizing the gravity potential difference.
In a preferred embodiment of the present invention, the mesh number of the filter is above 50, for example, the mesh number of the filter can be selected from 80 to 100.
According to the present invention, when the mesh number of the filter is within the range defined in the present application, it is advantageous to efficiently filter the cation exchange resin catalyst and to increase the content of the effective component in the reaction product.
The invention also provides a method for producing polymethoxy dimethyl ether, which comprises the following steps:
a) Introducing methylal and paraformaldehyde into a jacketed kettle type stirring reactor, and reacting the methylal and the paraformaldehyde in the presence of a catalyst to obtain a first reaction solution;
b) Cooling the first reaction liquid, enabling the first reaction liquid to flow out of the middle section or the middle-upper section of the jacket kettle type stirring reactor, and filtering the first reaction liquid through a filter to obtain a second reaction liquid;
c) Sending the second reaction liquid to a reaction liquid intermediate tank to obtain a third reaction liquid;
d) Enabling the third reaction solution to enter an anion resin neutralization tank for carrying out circulating neutralization reaction to obtain a fourth reaction solution containing the polyoxymethylene dimethyl ethers;
preferably, the pH of the fourth reaction solution is 6.7 to 7.5.
The inventor of the present application has found that, by allowing the reaction solution to enter the anion resin neutralization tank for a circulating neutralization reaction, corrosion of the reaction solution on equipment and polymerization of by-products in the reaction solution under acidic conditions can be prevented, and the subsequent rectification operation can be facilitated. Further, when the pH of the reaction solution reached 6.7 to 7.5, it was revealed that the reaction solution had a greatly reduced possibility of corroding the equipment and polymerization of by-products in the reaction solution under acidic conditions.
According to the present invention, more preferably, the pH of the fourth reaction liquid is 6.9 to 7.1.
According to the present invention, the cation exchange resin catalyst is selected from at least one of a solid acid catalyst, a cation resin catalyst and an acid catalyst. When the cation exchange resin catalyst is selected, the synthesis of the polymethoxy dimethyl ether product is facilitated.
According to the invention, the mass ratio of methylal to paraformaldehyde is (1-6.5): 1.
According to the invention, the cation exchange resin catalyst is used in an amount of 5 to 20% by weight, based on the total mass of methylal and paraformaldehyde.
In a preferred embodiment of the present invention, the polyoxymethylene dimethyl ethers production process further comprises:
e) After said step a) is completed, introducing methylal and paraformaldehyde into another jacketed kettle-type stirred reactor, and repeating steps a) -c).
According to the invention, the two reactors, particularly the jacketed kettle type stirring reactor, are matched for use, so that the reaction can be continuously carried out, the reaction time can be shortened, and the reaction efficiency can be improved.
In a preferred embodiment of the present invention, the reaction time of the reaction is 0.5 to 2 hours, preferably 0.5 to 1.5 hours.
According to the invention, when the reaction time is less than 0.5h, the PODE 3-5 The synthesis reaction of (2) is not fully completed; when the reaction time is more than 2h, the non-target component PODE 6-8 The composition will increase. Therefore, to balance the target product PODE 3-5 And non-target component PODE 6-8 The reaction time is controlled within the above range.
It will be appreciated that a reaction time of from 0.5h to 2h (or from 0.5h to 1.5 h) means that the reactor feed is switched between the two reactors for a time interval of from 0.5h to 2h (or from 0.5h to 1.5 h).
In a preferred embodiment of the invention, the reaction temperature of the reaction is from 80 ℃ to 140 ℃, preferably from 90 ℃ to 120 ℃.
According to the invention, when the reaction temperature is in the limited range of the application, the performance of the catalyst can be exerted to the maximum extent, and the synthesis of the target product polymethoxy dimethyl ether is facilitated.
According to the invention, the reaction temperature of the reaction is controlled by a heat medium, preferably heat transfer oil and low-pressure steam.
In a preferred embodiment of the present invention, the reaction pressure of the reaction is 300kPa to 800kPa, preferably 400kPa to 600kPa, preferably the reaction pressure is controlled by an inert gas, more preferably the inert gas is selected from at least one of nitrogen, argon and helium, more preferably the inert gas is nitrogen.
According to the invention, the stirring speed of the reaction is 300 r/min-900 r/min.
In a preferred embodiment of the present invention, the temperature of the temperature reduction treatment is 30 ℃ to 60 ℃.
According to the invention, the temperature reduction treatment comprises the step of removing heat and reducing the temperature of the reaction liquid through a cooling medium in the jacket.
According to the invention, the cooling medium is preferably heat transfer oil and low-pressure steam.
In a preferred embodiment of the present invention, the temperature of the reaction solution intermediate tank is 30 ℃ to 60 ℃, preferably 40 ℃ to 50 ℃; the pressure is 100kPa to 200kPa, preferably 100kPa to 150kPa.
In a preferred embodiment of the invention, the temperature of the cyclic neutralization reaction is between 30 ℃ and 60 ℃, preferably between 40 ℃ and 50 ℃; the pressure is 100kPa to 200kPa, preferably 100kPa to 150kPa; the time is 0.4 h-2 h, preferably 0.5 h-1 h.
By adopting the technical scheme of the invention, the synthesis reaction of paraformaldehyde and methylal can be effectively carried out, the continuous production is ensured by switching operation of the two reactors, and a good effect is obtained on the actual production of polymethoxy dimethyl ether.
Drawings
Fig. 1 is a schematic flow chart of example 1 and example 2.
Description of the reference numerals: i A, IB-jacket kettle type stirring reactors; II, reaction liquid intermediate tank; III-anion resin neutralization tank; VI-a reaction liquid collecting tank; v-circulation discharge pump; VII-filter.
1-methylal (dimethoymethane, abbreviated as DMM); 2-paraformaldehyde; 3-inert gas; 4-a first reaction solution; 5-a second reaction solution; 6-third reaction solution; 7-recycle feed to the anion neutralization tank; 8-discharge of the anion resin neutralization tank; 9-reaction liquid of an anion neutralization tank conveyed by a circulating discharge pump V; 10-fourth reaction liquid, 13 is hot medium feeding, 13 'is cold medium feeding, 14 is hot medium discharging, and 14' is cold medium discharging.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
Example 1
The method comprises the following steps: 141kg of paraformaldehyde (2) and 600kg of methylal (1) were introduced into a jacketed kettle-type stirred reactor (IA) having a volume of 2 cubic meters and containing 140kg of a cationic resin catalyst, the reaction temperature was controlled at 100 ℃ by feeding a heat transfer oil (13), the pressure was adjusted to 500kPa by nitrogen (3), and the reaction was continuously stirred at a rotation speed of 500r/min for 0.5h to prepare a first reaction solution (4).
Step two: and (3) removing heat and reducing temperature of the first reaction liquid (4) through heat conducting oil feeding (13'), discharging the first reaction liquid (4) from a discharge port (a discharge port is positioned at 60% height of a jacket kettle type stirring reactor) of the jacket kettle type stirring reactor (IA) after the temperature of the first reaction liquid (4) is reduced to 30 ℃, and filtering through a filter (VII) with the mesh number of 50 to obtain a second reaction liquid (5).
Step three: the second reaction solution (5) was allowed to flow into a reaction solution intermediate tank (II) having a height of 2.0m from the jacketed kettle-type stirred reactor IA by means of a gravity head, the temperature of the reaction solution intermediate tank was 45 ℃ and the pressure was 100 kPa), to prepare a third reaction solution (6).
Step four: after completion of the first step, 141kg of paraformaldehyde (2) and 600kg of methylal (1) were introduced into another jacketed kettle-type stirred reactor (IB, containing 140kg of cationic resin catalyst) having a volume of 2 cubic meters, and the same operations as in the first to third steps were carried out.
Step five: and (3) enabling the third reaction liquid (6) to enter an anion resin neutralization tank (III), circulating for 0.5h under the conditions that the temperature is 40 ℃ and the pressure is 100kPa under the action of a circulating discharge pump (V), detecting that a fourth reaction liquid (10) containing polyoxymethylene dimethyl ethers is prepared after the pH =6.9 of the reaction liquid (7-9) in the anion neutralization tank, and conveying the fourth reaction liquid (10) to a reaction liquid collection tank (VI) through the circulating discharge pump.
The one-way time of the whole reaction was 60 minutes, the conversion of paraformaldehyde was 88%, and the PODE in the fourth reaction solution (10) 3-4 The content of (B) is 16%.
Example 2
The method comprises the following steps: 160kg of paraformaldehyde (2) and 650kg of methylal (1) were introduced into a jacketed kettle-type stirred reactor (IA) having a volume of 2 cubic meters and containing 160kg of a cationic resin catalyst, the reaction temperature was controlled at 120 ℃ by feeding a heat transfer oil (13), the pressure was adjusted at 600kPa by nitrogen (3), and the reaction was continuously stirred at a rotation speed of 500r/min for 0.5 hour to obtain a first reaction solution (4).
Step two: and (3) removing heat and reducing temperature of the first reaction liquid (4) through heat conduction oil feeding (13'), discharging the first reaction liquid (4) from a discharge port (a discharge port is positioned at 55% of the height of the jacketed kettle type stirring reactor) of the jacketed kettle type stirring reactor (IA) after the temperature of the first reaction liquid (4) is reduced to 40 ℃, and filtering through a filter (VII) with the mesh number of 80 meshes to prepare a second reaction liquid (5).
Step three: the second reaction solution (5) was allowed to flow into a reaction solution intermediate tank (II) having a height of 2.0m from the jacket tank type stirred reactor IA at a temperature of 50 ℃ and a pressure of 110 kPa) under the action of a gravitational potential difference, to obtain a third reaction solution (6).
Step four: after completion of the first step, 160kg of paraformaldehyde (2) and 650kg of methylal (1) were fed into another jacketed kettle-type stirred reactor (IB with 160kg of cationic resin catalyst charged therein) having a volume of 2 cubic meters, and the same operations as in the first to third steps were carried out.
Step five: and (3) enabling the third reaction liquid (6) to enter an anion resin neutralization tank (III), circulating for 0.5h under the conditions that the temperature is 50 ℃ and the pressure is 110kPa under the action of a circulating discharge pump (V), detecting that a fourth reaction liquid (10) containing polyoxymethylene dimethyl ethers is prepared after the pH =6.9 of the reaction liquid (7-9) in the anion neutralization tank, and conveying the fourth reaction liquid (10) to a reaction liquid collection tank (VI) through the circulating discharge pump.
The one-way time of the whole reaction was 60 minutes, the conversion of paraformaldehyde was 90%, and the PODE in the fourth reaction solution (10) 3-4 The content of (B) is 18%.
Example 3
Polyoxymethylene dimethyl ethers were produced in the same manner as in example 2 except that the discharge port of the jacketed kettle stirred reactor (IA) was located at 45% of the height of the jacketed kettle stirred reactor.
As a result, the conversion of paraformaldehyde was 89%, and PODE was contained in the fourth reaction solution (10) 3-4 The content of (B) is 17%.
Example 4
Polyoxymethylene dimethyl ethers were produced in the same manner as in example 2 except that the mesh number of the filter VII was 45.
As a result, the conversion of paraformaldehyde was 89.5%, and PODE in the fourth reaction solution (10) 3-4 The content of (B) was 17.8%.
Example 5
Polyoxymethylene dimethyl ethers were produced in the same manner as in example 2 except that the height of the head difference between the reaction liquid intermediate tank II and the jacketed kettle-type stirred reactor IA was 1.0m.
As a result, the conversion of paraformaldehyde was 87%, and PODE was contained in the fourth reaction solution (10) 3-4 The content of (B) is 16%.
Example 6
Polyoxymethylene dimethyl ethers were produced in the same manner as in example 2 except that:
step five: and (3) feeding the third reaction liquid (6) into an anion resin neutralization tank (III), circulating for 0.5h under the conditions that the temperature is 70 ℃ and the pressure is 90kPa under the action of a circulating discharge pump (V), detecting that a fourth reaction liquid (10) containing the polyoxymethylene dimethyl ethers is prepared after the pH =6.5 of the reaction liquid (7-9) in the anion neutralization tank, and conveying the fourth reaction liquid (10) to a reaction liquid collection tank (VI) through the circulating discharge pump.
As a result, the conversion of paraformaldehyde was 90%, and PODE was contained in the fourth reaction solution (10) 3-4 The content of (B) is 18%. Despite the conversion of paraformaldehyde and PODE 3-4 The content of (A) was equivalent to that in example 2, but the reaction solution easily corroded the apparatus, and by-products in the reaction solution were polymerized under acidic conditions.
Comparative example 1
A stirred reaction batch reactor was used.
Each time, 400kg of paraformaldehyde and 1500kg of methylal were charged into 3 parallel stirred batch reactors (each containing 40kg of 001x7 strongly acidic styrene cation exchange resin) having a volume of 1 cubic meter, reacted at a reaction temperature of 110 ℃ and a reaction pressure of 500kPa for 4 hours, and then fed into a separation unit.
The detection shows that the conversion rate of paraformaldehyde is 70 percent, and the PODE in the reaction solution 3-5 Only 20 percent.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (18)
1. A polymethoxy dimethyl ether production system, comprising:
a reactor;
a filter connected to the reactor;
the reaction liquid intermediate tank is connected with the filter; and
an anion resin neutralization tank connected with the reaction liquid intermediate tank;
the discharge hole of the reactor is positioned at 40-80% of the height of the reactor.
2. The polyoxymethylene dimethyl ether production system of claim 1, wherein the discharge port is located at 50-70% of the height of the reactor.
3. The polyoxymethylene dimethyl ether production system of claim 2, wherein the discharge port is located at 60-70% of the height of the reactor.
4. The polyoxymethylene dimethyl ether production system according to any one of claims 1 to 3, wherein a level difference between the reactor and the reaction liquid intermediate tank is not less than 1.5m in height.
5. The polyoxymethylene dimethyl ether production system of claim 4, wherein the reactor is a stirred tank reactor having heat tracing and heat removal functions.
6. The polymethoxy dimethyl ether production system according to any one of claims 1 to 3, wherein the filter has a mesh number of 50 or more.
7. A method for producing polyoxymethylene dimethyl ethers comprises the following steps:
a) Introducing methylal and paraformaldehyde into a reactor, and reacting the methylal and the paraformaldehyde in the presence of a catalyst to obtain a first reaction solution;
b) Cooling the first reaction liquid, enabling the first reaction liquid to flow out of the middle section or the middle-upper section of the reactor, and filtering the first reaction liquid through a filter to obtain a second reaction liquid;
c) Sending the second reaction liquid to a reaction liquid intermediate tank to obtain a third reaction liquid;
d) And enabling the third reaction solution to enter an anion resin neutralization tank for circulating neutralization reaction to obtain a fourth reaction solution containing the polyoxymethylene dimethyl ethers.
8. The process for producing polymethoxy dimethyl ether according to claim 7, wherein the pH of the fourth reaction liquid is from 6.7 to 7.5.
9. The method for producing polymethoxy dimethyl ether according to claim 7 or 8, further comprising:
e) After said step a) is completed, feeding methylal and paraformaldehyde into another reactor, and repeating steps a) -c).
10. The method for producing polyoxymethylene dimethyl ethers according to claim 7 or 8, wherein the reaction time of the reaction in step a) is 0.5 to 2 hours; and/or the reaction temperature is 80-140 ℃; and/or the reaction pressure is 300kPa to 800kPa.
11. The method for producing polymethoxy dimethyl ether according to claim 10, wherein in step a), the reaction time of the reaction is 0.5 to 1.5 hours; and/or the reaction temperature is 90-120 ℃ and/or the reaction pressure is 400-600 kPa.
12. The process for producing polymethoxy dimethyl ether according to claim 11, wherein the reaction pressure is controlled by inert gas.
13. The process for producing polymethoxy dimethyl ether according to claim 12, wherein the inert gas is at least one selected from the group consisting of nitrogen, helium and argon.
14. The process for producing polyoxymethylene dimethyl ethers according to claim 7 or 8,
in the step b), the temperature of the temperature reduction treatment is 30-60 ℃.
15. The method for producing polymethoxy dimethyl ether according to claim 7 or 8, wherein the temperature of the reaction liquid intermediate tank is 30 ℃ to 60 ℃; the pressure is 100kPa to 200kPa.
16. The method for producing polymethoxy dimethyl ether according to claim 15, wherein the temperature of the reaction liquid intermediate tank is 40 ℃ to 50 ℃; the pressure is 100kPa to 150kPa.
17. The polyoxymethylene dimethyl ether production process according to claim 7 or 8, wherein the temperature of the circulating neutralization reaction is 30 ℃ to 60 ℃; the pressure is 100kPa-200kPa; the time is 0.4 h-2 h.
18. The process for producing polyoxymethylene dimethyl ethers according to claim 17, wherein the temperature of the recycle neutralization reaction is 40 ℃ to 50 ℃; the pressure is 100kPa to 150kPa.
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| CN106588587A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Method for producing formaldehyde dimethyl ether with paraformaldehyde |
| CN107778149A (en) * | 2016-08-26 | 2018-03-09 | 张也贤 | The method for preparing polymethoxy dimethyl ether |
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| WO2006045506A1 (en) * | 2004-10-25 | 2006-05-04 | Basf Aktiengesellschaft | Method for producing polyoxymethylene dimethyl ethers |
| CN104725202A (en) * | 2015-03-24 | 2015-06-24 | 江苏凯茂石化科技有限公司 | Process device and method for production of poly methoxy dimethyl ether raw material |
| CN104817437A (en) * | 2015-05-14 | 2015-08-05 | 江苏凯茂石化科技有限公司 | Dehydration technique and dehydration device for synthesizing poly-methoxy-dimethyl ether |
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