CN103772166A - Preparation method of polyoxymethylene dimethyl ethers - Google Patents

Preparation method of polyoxymethylene dimethyl ethers Download PDF

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Publication number
CN103772166A
CN103772166A CN201210412604.8A CN201210412604A CN103772166A CN 103772166 A CN103772166 A CN 103772166A CN 201210412604 A CN201210412604 A CN 201210412604A CN 103772166 A CN103772166 A CN 103772166A
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dimethyl ether
polyoxymethylene dimethyl
preparation
zsm
acid
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何欣
袁志庆
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a preparation method of polyoxymethylene dimethyl ethers, which mainly solves the problem that a catalyst in the prior art has corrosivity. The method comprises the steps that methanol or dimethyl ether and methanal or trioxymethylene serve as raw materials; a mole ratio of methanol or dimethyl ether to methanal or trioxymethylene is 1:(0.1-10); the raw reaction materials are contacted with a catalyst at reaction temperature of 50-200 DEG C and reaction pressure of 0.1-10MPa; and the polyoxymethylene dimethyl ethers are generated. The catalyst comprises the following components in parts by weight: a) 40-95 parts of ZSM-11 molecular sieve with a mole ratio of SiO2/Al2O3 of 20-300 and the crystal grain diameter less than or equal to 5 micrometers, and b) 5-60 parts of binding agent; and the ZSM-11 molecular sieve is at least subjected to acid pickling once. With the adoption of the technical scheme, the problem is solved better, so that the method can be used in industrial production of the polyoxymethylene dimethyl ethers.

Description

The preparation method of polyoxymethylene dimethyl ether
Technical field
The present invention relates to a kind of preparation method of polyoxymethylene dimethyl ether.
Background technology
(Chinese can be also polyoxymethylene dimethyl ether to polyoxymethylene dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, polymethoxy dimethyl ether, polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers etc.), i.e. polyoxymethylene dimethyl ethers (PODE), it is the common name of a class material, and its molecular structural formula is CH 3o (CH 2o) ncH 3, there is higher cetane value (cetane number, CN.N=3～8 o'clock, CN>76) and oxygen level (42～49%).In the time that the value of n is 3～8, its physical and chemical performance, combustionproperty and diesel oil are very approaching, can be used as diesel-dope, and the addition in diesel oil can reach 30% (v/v), keep higher cetane value and combustionproperty simultaneously.Can improve the oilness of diesel oil, reduce combustion fumes and generate, can improve the combustion position of diesel oil in engine, improve thermo-efficiency, reduce particulate matter and NO in combustion tail gas xdischarge.Also possibility diesel oil substitute, directly as diesel-fuel.
Polyoxymethylene dimethyl ether is to solve dme to make the defect that derv fuel oil blend component exists as the main purpose of Novel clean oil dope research and development.Rich coal resources in China, has strategic importance and good economic worth by coal-based methanol combined diesel oil blend component, is day by day subject to people's attention.
US2449469 discloses a kind of take methylal and paraformaldehyde as raw material, prepares the method for the polyoxymethylene dimethyl ether of n=2～4, but have the problem that catalytic erosion is serious using sulfuric acid as catalyzer.
WO2006/045506A1 discloses BASF AG and has used sulfuric acid or trifluoromethanesulfonic acid as catalyzer, take methyl alcohol, methylal, trioxymethylene, paraformaldehyde etc. as raw material, has obtained the series product of n=1～10, has equally the problem that catalytic erosion is serious.
US5746785 discloses a kind of take 0.1wt% formic acid as catalyzer, and take methylal and paraformaldehyde or methyl alcohol and paraformaldehyde as raw material, the series product of preparation n=1～10, exist the problem that catalytic erosion is serious equally.
CN101182367A and CN101962318A disclose employing acidic ion liquid as catalyzer, are the method that raw material is prepared polyoxymethylene dimethyl ether by methyl alcohol and trioxymethylene, have equally the problem that catalytic erosion is serious.
CN101665414A discloses a kind of employing acidic ion liquid as catalyzer, is the method that raw material is prepared polyoxymethylene dimethyl ether by methylal and trioxymethylene, has equally the problem that catalytic erosion is serious.
In sum, the catalyzer adopting in conventional art has corrosive shortcoming.
Summary of the invention
Technical problem to be solved by this invention is in conventional art, to exist catalyzer to have corrosive problem, and a kind of preparation method of new polyoxymethylene dimethyl ether is provided.The method has the free from corrosion advantage of catalyzer.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of polyoxymethylene dimethyl ether, take methyl alcohol or dme and formaldehyde or trioxymethylene as raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1～10, it is 50～200 ℃ in temperature of reaction, reaction pressure is under 0.1～10MPa condition, and reaction raw materials contacts with catalyzer and generates polyoxymethylene dimethyl ether; Catalyst levels is 0.01～15% of reaction raw materials weight; Wherein catalyzer used, in parts by weight, comprises following component:
A) the silica alumina ratio SiO of 40～95 parts 2/ Al 2o 3be 20～300, the ZSM-11 molecular sieve of crystal grain diameter≤5 micron;
B) binding agent of 5～60 parts;
Described ZSM-11 molecular sieve is that the acid of 0.1～2 mol/L is processed at least one times under 70～90 ℃ of conditions by concentration, each acid treatment time is 2～10 hours, wherein acid is 1～20 with the weight ratio of ZSM-11 molecular sieve, and acid is selected from least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or citric acid.
In technique scheme, the crystal grain diameter preferable range of ZSM-11 molecular sieve is 0.1～5, and more preferably scope is 0.1～2 micron.The silica alumina ratio SiO of ZSM-11 molecular sieve 2/ Al 2o 3preferable range is 40～150.Described binding agent preferred version is at least one being selected from aluminum oxide or boehmite.Described ZSM-11 molecular sieve preferred version is synthetic by following method: with water glass, at least one in silicon sol or White Carbon black is silicon source, with sodium metaaluminate, at least one in Tai-Ace S 150 or aluminum nitrate is aluminium source, with Tetrabutyl amonium bromide, tetrabutylammonium chloride, at least one in tetrabutylammonium iodide or TBAH is template, with sodium hydroxide, at least one in potassium hydroxide or ammoniacal liquor is alkali source, take at least one in sodium-chlor or Repone K as metal-salt, by silicon source, aluminium source, alkali source, template, metal-salt and water mix plastic, reaction mixture is take molar ratio computing as SiO 2/ Al 2o 3=20～300, H 2o/SiO 2=10～150, Cl -/ SiO 2=0.01～5, OH -/ SiO 2=0.001～1, template/SiO 2=0.01～1, under 100～200 ℃ of conditions of crystallization temperature, crystallization 0.5～16 day, crystallized product after filtration, washing, obtain described ZSM-11 molecular sieve after dry.The constitutive molar ratio preferable range of reaction mixture is SiO 2/ Al 2o 3=40～150, H 2o/SiO 2=30～80, Cl -/ SiO 2=0.1～1, OH -/ SiO 2=0.05～0.5, template/SiO 2=0.1～0.5.Crystallization temperature preferable range is 120～180 ℃, and crystallization time preferable range is 1～10 day.
Methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio preferable range are 1:0.5～6.Formaldehyde can be the formaldehyde solution of 10～80wt%, or paraformaldehyde or trioxymethylene.Catalyst levels is that the preferable range of reaction raw materials weight is 0.1～10%.Temperature of reaction preferable range is 70～150 ℃, and reaction pressure preferable range is 0.5～6MPa.
The preparation method of catalyzer in the present invention: by the acid treatment of ZSM-11 molecular sieve at least one times, dry rear and binding agent mixing moulding, then 80～150 ℃ dry 5～24 hours, 400～700 ℃ of roastings 3～10 hours, pelletizing obtains the catalyzer of preparing polyoxymethylene dimethyl ether.
ZSM-11 molecular sieve is a member in high-silicon ZSM-5 series, being that oval ten-ring two-dimensional direct duct (0.51 × 0.55nm) is crossing forms, belong to micro-pore zeolite, because it does not have cage, so be difficult for carbon distribution in catalytic process, and have fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity.The present invention is by adopting fine grain ZSM-5-11 molecular sieve of crystal grain diameter≤5 micron as the active ingredient of catalyzer, because the ZSM-11 molecular sieve of little crystal grain is compared conventional ZSM-11 molecular sieve and had larger external surface area and higher intracrystalline rate of diffusion, all show superior performance improving the utilization ratio of catalyzer, strengthen macromole conversion capability, reduce deep reaction, improve selectivity and reduce the aspects such as coking and deactivation.In addition, in the present invention, use acid at 70～90 ℃, ZSM-11 molecular sieve to be processed, can play certain regulating effect to the distribution of the Acidity of molecular sieve catalyst, B acid, L acid and strong and weak acid on the one hand; Can remove on the other hand amorphous substance in molecular sieve pore passage or remove the materials such as the non-framework aluminum that gets off from framework of molecular sieve, make originally fully to be exposed by amorphous active centre of waiting material to cover in molecular sieve pore passage, play the modification to molecular sieve pore passage, activity of molecular sieve catalysts is increased to some extent, the burnt ability of appearance of catalyzer improves greatly, and activity stability has had very large improvement.In addition, acid treatment also can further reduce the sodium content of catalyzer, is useful to the activity and the stability that improve catalyzer.The inventor finds uncannily, adopts the inventive method, under 130 ℃ of temperature, pressure 6MPa, reacts 2 hours, and the product that n is 3～8 can reach 32.2% in products distribution; The most important thing is that catalyzer non-corrosiveness has been obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of [embodiment 1] synthetic fine grain ZSM-5-11 molecular sieve.
Fig. 2 is the SEM photo of [embodiment 1] synthetic fine grain ZSM-5-11 molecular sieve.
In Fig. 1, X-ray diffracting spectrum is 23.0,23.9, and there is strong diffraction peak at 7.9,8.8 and 45.1 degree places, illustrates that this zeolite has MEL topological framework, is ZSM-11 zeolite.
In Fig. 2, can be found out by SEM photo, the average crystal grain diameter of this ZSM-11 zeolite is 0.5 micron.
 
Below by embodiment, the present invention is further elaborated.
 
Embodiment
[embodiment 1]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium-chlor, sodium hydroxide and water are mixed, stir 20 minutes, pack in reactor, 170 ℃ of crystallization 1 day.Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 ℃, makes ZSM-11 molecular screen primary powder, and XRD spectra is shown in Fig. 1, and Fig. 2 is shown in by SEM photo, and crystal grain diameter is 0.5 micron.In reaction mixture, the mol ratio of each raw material is: SiO 2/ Al 2o 3=149.3, H 2o/SiO 2=32.8, NaCl/SiO 2=0.6, NaOH/SiO 2=0.08, TBABr/SiO 2=0.12.
Synthetic ZSM-11 molecular screen primary powder is processed 4 hours at 80 ℃ with 0.3 mol/L nitric acid, continuous 3 times, obtained HZSM-11.
HZSM-11 is mixed with boehmite, field mountain valley with clumps of trees and bamboo powder, 0.3 mol/L nitric acid, and the weight ratio of each raw material is ZSM-11/Al 2o 3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1, extruded moulding, dries 12 hours in 120 ℃, 550 ℃ of roastings 5 hours, pelletizing, obtains the catalyzer of moulding.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 2 grams of catalyzer, 100 grams of methyl alcohol, 100 grams of trioxymethylenes, at 130 ℃ with make pressure by inflated with nitrogen be to react under 6MPa 2 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
 
[embodiment 2]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium-chlor, sodium hydroxide and water are mixed, stir 20 minutes, pack in reactor, 170 ℃ of crystallization 1 day.Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 ℃, makes ZSM-11 molecular screen primary powder, and crystal grain diameter is 0.5 micron.In reaction mixture, the mol ratio of each raw material is: SiO 2/ Al 2o 3=149.3, H 2o/SiO 2=32.8, NaCl/SiO 2=0.6, NaOH/SiO 2=0.08, TBABr/SiO 2=0.12.
Synthetic ZSM-11 molecular screen primary powder is processed 4 hours at 80 ℃ with 0.3 mol/L hydrochloric acid, continuous 3 times, obtained HZSM-11.
HZSM-11 is mixed with boehmite, field mountain valley with clumps of trees and bamboo powder, 0.3 mol/L nitric acid, and the weight ratio of each raw material is HZSM-11/Al 2o 3/ field mountain valley with clumps of trees and bamboo powder=1:1:0.1, extruded moulding, dries 12 hours in 120 ℃, 550 ℃ of roastings 5 hours, pelletizing, obtains the catalyzer of moulding.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1.5 grams of catalyzer, 80 grams of dme, 100 grams of trioxymethylenes, at 110 ℃ with make pressure by inflated with nitrogen be to react under 4MPa 4 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
 
[embodiment 3]
By each Step By Condition of [embodiment 2], just SiO in synthesizing formula 2/ Al 2o 3=52, template adopts TBAH, 120 ℃ of crystallization of crystallization temperature 8 days, and synthetic ZSM-11 molecular screen primary powder crystal grain diameter is 1 micron.With 1.0 mol/L citric acids 80 ℃ exchange 10 hours.Obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1.2 grams of catalyzer, 50 grams of methyl alcohol, 50 grams of dme, 100 grams of trioxymethylenes, at 100 ℃ with make pressure by inflated with nitrogen be to react under 1MPa 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
 
[embodiment 4]
By each Step By Condition of [embodiment 2], just synthesizing formula Raw, batching proportioning difference.Aluminium source is Tai-Ace S 150, and silicon source is water glass, and template is TBAH.In reaction mixture, the mol ratio of each raw material is: SiO 2/ Al 2o 3=80.9, H 2o/SiO 2=58.5, NaCl/SiO 2=0.80, NaOH/SiO 2=0.30, TBAOH/SiO 2=0.19.The ZSM-11 molecular screen primary powder crystal grain diameter making is 0.8 micron.Obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 100 grams of dme, 90 grams of formaldehyde, at 80 ℃ with make pressure by inflated with nitrogen be to react under 2MPa 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
 
[comparative example 1]
By each Step By Condition of [embodiment 1], just do not add NaCl.The ZSM-11 molecular screen primary powder average crystal grain diameter making is 11 microns.Obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction result is in table 1.
 
[comparative example 2]
By each Step By Condition of [comparative example 1], acid treatment is with [embodiment 3].Obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction result is in table 1.
 
[comparative example 3]
Adopt the former powder of certain industrial ZSM-5, its average crystal grain diameter is 10 microns, after processing, obtains catalyzer by the method in [embodiment 2].
By the performance of each step evaluate catalysts of [embodiment 1], reaction result is in table 1.
Table 1
Figure 28683DEST_PATH_IMAGE002

Claims (9)

1. the preparation method of a polyoxymethylene dimethyl ether, take methyl alcohol or dme and formaldehyde or trioxymethylene as raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1～10, it is 50～200 ℃ in temperature of reaction, reaction pressure is under 0.1～10MPa condition, and reaction raw materials contacts with catalyzer and generates polyoxymethylene dimethyl ether; Catalyst levels is 0.01～15% of reaction raw materials weight; Wherein catalyzer used, in parts by weight, comprises following component:
A) the silica alumina ratio SiO of 40～95 parts 2/ Al 2o 3be 20～300, the ZSM-11 molecular sieve of crystal grain diameter≤5 micron;
B) binding agent of 5～60 parts;
Described ZSM-11 molecular sieve is that the acid of 0.1～2 mol/L is processed at least one times under 70～90 ℃ of conditions by concentration, each acid treatment time is 2～10 hours, wherein acid is 1～20 with the weight ratio of ZSM-11 molecular sieve, and acid is selected from least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or citric acid.
2. the preparation method of polyoxymethylene dimethyl ether according to claim 1, the crystal grain diameter that it is characterized in that ZSM-11 molecular sieve is 0.1～5 micron.
3. the preparation method of polyoxymethylene dimethyl ether according to claim 2, the crystal grain diameter that it is characterized in that ZSM-11 molecular sieve is 0.1～2 micron.
4. the preparation method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that described binding agent is selected from least one in aluminum oxide or boehmite.
5. the preparation method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that the silica alumina ratio SiO of ZSM-11 molecular sieve 2/ Al 2o 3be 40～150.
6. the preparation method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.5～6.
7. the preparation method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that formaldehyde can be the formaldehyde solution of 10～80wt%, or paraformaldehyde or trioxymethylene.
8. the preparation method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that catalyst levels is 0.1～10% of reaction raw materials weight.
9. the preparation method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that temperature of reaction is 70～150 ℃, and reaction pressure is 0.5～6MPa.
CN201210412604.8A 2012-10-25 2012-10-25 Preparation method of polyoxymethylene dimethyl ethers Pending CN103772166A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040488A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Method for synthesizing PODE (polyformaldehyde dimethyl ether)
CN103539644A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Preparation method of polyoxy methylene dimethyl ether

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040488A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Method for synthesizing PODE (polyformaldehyde dimethyl ether)
CN103539644A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Preparation method of polyoxy methylene dimethyl ether

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Application publication date: 20140507