CN105237366A - Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve - Google Patents
Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve Download PDFInfo
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- CN105237366A CN105237366A CN201510557855.9A CN201510557855A CN105237366A CN 105237366 A CN105237366 A CN 105237366A CN 201510557855 A CN201510557855 A CN 201510557855A CN 105237366 A CN105237366 A CN 105237366A
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- dimethyl ether
- vitriol
- catalyze
- synthesize
- polyoxymethylene dimethyl
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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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Abstract
The invention belongs to the field of preparation of diesel additives and especially relates to a method of catalytically preparing polyformaldehyde dimethyl ether through an acidic catalyst formed by supporting sulfates on a molecular sieve, which is denoted by SO<4><2->/HY. In a high-pressure reaction kettle, polyformaldehyde, methylal, and the acidic catalyst formed by supporting one or more sulfates on the molecular sieve are added with nitrogen fed for protection. Under magnetic stirring, the reaction kettle is heated to carry out a reaction, and after the reaction is finished, the products are centrifugally separated to obtain supernatant liquid. The acidic catalyst is free of pollution and is easy to recycle, is high in repeatability rate, shows a high catalytic activity, and is high in activity and selectivity when compared with ionic liquids and molecular sieves individually.
Description
Technical field
The invention belongs to diesel-dope preparation field, particularly relate to a kind of an acidic catalyst by molecular sieve carried vitriol and (be denoted as SO
4 2-/ HY) catalyze and synthesize the method for polyoxymethylene dimethyl ether.
Background technology
The substrate catalyzed and synthesized selected by polyoxymethylene dimethyl ether is generally a kind of combination wherein of a kind of and paraformaldehyde, the trioxymethylene etc. wherein such as methyl alcohol, methylal, generates product polyoxymethylene dimethyl ether DMM
n, the serial DMM of n from 1 to 10
nproduct.DMM
3-8there is higher cetane value (CN>76) and oxygen level (45% ~ 51%); Good with the mutual solubility of diesel oil, be considered to a kind of excellent diesel oil and mix burning component, directly can add in diesel oil and not need to transform engine interior; In diesel oil, add 10% ~ 30%, significantly can reduce the discharge of NO, CO and some particulate matter in tail gas, and significantly can increase the oilness of diesel oil; Be considered to a kind of novel environment friendly diesel oil addO-on therapy having application prospect.
In prior art, the technique catalyzing and synthesizing polyoxymethylene dimethyl ether is high to catalyst requirement, and making step is more loaded down with trivial details, and some is large to reaction vessel corrodibility, not easily reclaim, and selectivity is low.
Summary of the invention
The present invention is complicated at existing catalyst preparing, and the selectivity catalyzing and synthesizing polyoxymethylene dimethyl ether is lower, and after having reacted, the defect such as not easily separated, provides a kind of an acidic catalyst of molecular sieve carried vitriol (to be denoted as SO
4 2-/ HY) catalyze and synthesize the method for polyoxymethylene dimethyl ether.
The technical solution adopted in the present invention is: an acidic catalyst adding paraformaldehyde, methylal, molecular sieve carried a kind of vitriol or multiple vitriol in autoclave; pass into nitrogen protection; heating is reacted under magnetic stirring; react rear to product centrifugation, got supernatant liquid and be polyoxymethylene dimethyl ether (DMM
n),
Wherein, the mass ratio of reactant methylal and paraformaldehyde between 1:4 ~ 1:2,
The consumption of an acidic catalyst of molecular sieve carried a kind of vitriol or multiple vitriol is 0.5% ~ 5% of reactant methylal and the paraformaldehyde total mass added,
Passing into nitrogen pressure is 1MPa ~ 2MPa,
The Heating temperature of reaction is 110 DEG C ~ 130 DEG C, and the magnetic agitation time is 3h ~ 12h;
The preparation method of above-mentioned molecular sieve carried a kind of vitriol or an acidic catalyst of multiple vitriol is:
Vitriol and Hydrogen Y zeolite (Y zeolite of H type) are placed in beaker, add deionized water, then the sulfuric acid that Solute mass concentration is 5% ~ 10% is added dropwise to, room temperature (25 DEG C) suction filtration is cooled to after 80 DEG C ~ 120 DEG C heated and stirred 4 ~ 6h, with deionized water rinsing to the liquid pH flushed out in neutral, dry 4h ~ 5h at putting into 90 DEG C ~ 110 DEG C, baking oven, cooling, obtains catalyst S O
4 2-/ HY,
As preferably: Y zeolite is silica alumina ratio is 1:(10 ~ 40) Hydrogen Y zeolite, self there is certain acidity;
As preferably: the mass ratio of Y zeolite and vitriol is 2:1 ~ 5:1,
Above-mentioned vitriol is Al
2(SO
4)
3, CdSO
4, CuSO
4, SrSO
4, Fe
2(SO
4)
3, MnSO
4, Ce
2(SO
4)
3, FeSO
4, CaSO
4, ZnSO
4, NiSO
4, CoSO
4, CrSO
4or MgSO
4,
HY type molecular sieve prepared by Zibo Dai Qi environment project company limited is adopted in the present invention.
The present invention compared with prior art has the following advantages: for catalyzer (sulfuric acid, tosic acid), have environmental protection relative to some strong acid, not perishable container, can repeatedly use and transformation efficiency and selectivity can keep the advantage such as better.Reactivity worth for catalysis methylal and paraformaldehyde synthesizing polyoxymethylene dme is better.An acidic catalyst SO of molecular sieve carried vitriol
4 2-vitriol and molecular sieve are combined as catalyzer by both chemical bondings by/HY, and pollution-free, easily reclaim, repeat usage is higher, shows higher catalytic activity, than being used alone ionic liquid and molecular sieve catalytic active is high, selectivity is good.Molecular sieve is carrier, is also active ingredient, an acidic catalyst SO of sulfur loaded hydrochlorate
4 2-/ HY preparation process is simple, easily reclaims, can repeatedly use, show good stability and catalytic activity.Catalyst preparation process is uncomplicated, pollution-free, transformation efficiency and selectivity are all high than directly using molecular sieve or ionic liquid to make catalyst synthesizing polyoxymethylene dme, use molecular sieve carried sulfate catalyst, transformation efficiency all can reach more than 99% (with the transformation efficiency of paraformaldehyde for benchmark), basic complete reaction.
Embodiment
Comparative example 1
Hydrogen Y zeolite is taken 0.5g as catalyzer, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 13.8%.
Comparative example 2
By macropore strong acid cation exchange resin (CT175) catalyzer 0.5g, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 19.8%.
Comparative example 3
Take 5 grams of pyridine mesylate ionic liquids in there-necked flask, add 3g coupling agent 3-chloropropyl triethoxysilane, then add and dilute with the mixed solution of the dehydrated alcohol of water volume ratio 6:1, stir when bath temperature is 80 DEG C, back flow reaction, the time is 6h.Then add the HZSM-5 molecular sieve that takes in there-necked flask, continue stirring reaction 6h.Reacted with dehydrated alcohol repetitive scrubbing repeatedly, revolve and steam about 30min, with husky star funnel suction filtration, use deionized water repetitive scrubbing, until taking out till water pH test paper caught on a filter test is neutrality, finally putting into baking oven and drying 5h at 110 DEG C.So far, catalyst reaction completes, and is designated as IL-mod/HZSM-5.
The catalyzer made is taken 0.5g, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 20.8%.
Comparative example 4
Make solid super-strong acid SO
4 2-/ Fe
2o
3catalyzer is as follows: add Fe at the sulphuric acid soln 200ml of 5%
2o
310 grams with the FeSO of 10 grams
4, stir 3h at normal temperatures, suction filtration deionized water rinsing is neutral to the test of pH test paper, dries to constant weight, obtains solid super-strong acid SO
4 2-/ Fe
2o
3catalyzer.
The catalyzer made is taken 0.5g, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 20.4%.
Embodiment 1
Take 1 gram of Al
2(SO
4)
3the Y zeolite of salt and 5 grams of H types is in beaker, add the deionized water of 50mL, then progressively drip the sulfuric acid 1g that mass concentration is 8%, stir, be heated to 80 DEG C, stir 4h, cooling suction filtration, a large amount of deionized water rinsing of filter cake, flushing repeatedly, till the liquid pH test paper test display neutrality flushed out, dry 2h at 60 DEG C, cooling.So far, catalyst reaction completes, and is designated as Al
2(SO
4)
3/ HY.
The good catalyzer of preparation is taken 0.5g, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 35.1%.
Embodiment 2
Take CdSO
4the Y zeolite of 2 grams and 6 grams H types is in beaker, add the deionized water of 50mL, then progressively drip the sulfuric acid 2g that mass concentration is 8%, stir, be heated to 80 DEG C, stir 4h, cooling suction filtration, a large amount of deionized water rinsing of filter cake, flushing repeatedly, till the liquid pH test paper test display neutrality flushed out, dry 3h at 80 DEG C, cooling.So far, catalyst reaction completes, and is designated as CdSO
4/ HY.
The good catalyzer of preparation is taken 0.9g, add 10g methylal and 30g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 4h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 32.5%.
Embodiment 3
Take CuSO
43 grams, SrSO
4the Y zeolite of 1.5 grams and 8 grams H types is in beaker, add the deionized water of 50mL, then progressively drip the sulfuric acid 3g that mass concentration is 8%, stir, be heated to 100 DEG C, stir 4h, cooling suction filtration, a large amount of deionized water rinsing of filter cake, flushing repeatedly, till the liquid pH test paper test display neutrality flushed out, dry 4h at 100 DEG C, cooling.So far, catalyst reaction completes, and is designated as CuSO
4, SrSO
4/ HY.
The good catalyzer of preparation is taken 0.7g, add 10g methylal and 25g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 6h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 30.1%.
Embodiment 4
Take Fe
2(SO
4)
3, MnSO
4the Y zeolite of each 2 grams and the 10 grams H types of salt is in beaker, add the deionized water of 50mL, then progressively drip the sulfuric acid 4g that mass concentration is 8%, stir, be heated to 110 DEG C, stir 5h, cooling suction filtration, a large amount of deionized water rinsing of filter cake, flushing repeatedly, till the liquid pH test paper test display neutrality flushed out, dry 5h at 110 DEG C, cooling.So far, catalyst reaction completes, and is designated as Fe
2(SO
4)
3, MnSO
4/ HY.
The good catalyzer of preparation is taken 0.5g and puts into 100mL autoclave, add 10g methylal and 20g paraformaldehyde, passing into nitrogen pressure is 2MPa, control temperature 120 DEG C, whole reaction heated and stirred 8h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 32.7%.
Embodiment 5
Take Ce
2(SO
4)
33 grams, FeSO
41 gram, CaSO
4the Y zeolite of 1 gram and 10 grams H type is in beaker, add the deionized water of 50mL, then progressively drip the sulfuric acid 5g that mass concentration is 8%, stir, be heated to 120 DEG C, stir 6h, cooling suction filtration, a large amount of deionized water rinsing of filter cake, flushing repeatedly, till the liquid pH test paper test display neutrality flushed out, dry 5h at 110 DEG C, cooling.So far, catalyst reaction completes, and is designated as Ce
2(SO
4)
3, FeSO
4, CaSO
4/ HY.
The good catalyzer of preparation is taken 1.2g, add 10g methylal and 20g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 2MPa, control temperature 130 DEG C, whole reaction heated and stirred 10h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 29.6%.
Embodiment 6
Take ZnSO
4, NiSO
4, CoSO
4, CrSO
4the Y zeolite of each 1 gram and 12 grams H type is in beaker, add the deionized water of 50mL, then progressively drip the sulfuric acid 6g that mass concentration is 8%, stir, be heated to 130 DEG C, stir 6h, cooling suction filtration, a large amount of deionized water rinsing of filter cake, flushing repeatedly, till the liquid pH test paper test display neutrality flushed out, dry 5h at 100 DEG C, cooling.So far, catalyst reaction completes, and is designated as ZnSO
4, NiSO
4, CoSO
4, CrSO
4/ HY.
The good catalyzer of preparation is taken 1.0g, add 10g methylal and 25g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 2MPa, control temperature 140 DEG C, whole reaction heated and stirred 12h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, detected result DMM
3-8content is 28.1%.
Embodiment 7 (revision test)
By the Al in embodiment 1
2(SO
4)
3/ HY catalyzer is separated from reaction product, uses deionized water rinsing suction filtration, rinses 3 times, dries 7h at 100 DEG C, cooling.The Al reclaimed
2(SO
4)
3/ HY catalyzer 0.45g, adds fresh Al
2(SO
4)
3/ HY catalyzer 0.05g adds up to 0.5g, add 10g methylal and 40g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, and detected result is as following table.After having reacted, above step repeats 5 times, carries out 5 repeated experiments altogether.
| Reaction times | x(TRIox)(％) |
| 1 | 35.1 |
| 2 | 34.7 |
| 3 | 34.6 |
| 4 | 34.5 |
| 5 | 34.1 |
| 6 | 33.9 |
Embodiment 8 (revision test)
By the Fe in embodiment 4
2(SO
4)
3/ MnSO
4/ HY catalyzer is separated from reaction product, uses deionized water rinsing suction filtration, rinses 3 times, dries 7h at 120 DEG C, cooling.The Fe reclaimed
2(SO
4)
3/ MnSO
4/ HY catalyzer 0.4g, adds fresh Fe
2(SO
4)
3/ MnSO
4/ HY catalyzer 0.1g adds up to 0.5g, add 10g methylal and 30g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 2MPa, control temperature 120 DEG C, whole reaction heated and stirred 8h, leaves standstill and is cooled to normal temperature 25 DEG C, and catalyzer is removed in centrifugation, gas-chromatography is analyzed, and detected result is as following table.Repeat above step 5 time after having reacted, carry out 5 repeated experiments altogether.
| Reaction times | x(TRIox)(％) |
| 1 | 32.7 |
| 2 | 31.7 |
| 3 | 31.6 |
| 4 | 31.5 |
| 5 | 30.1 |
| 6 | 29.9 |
Claims (9)
1. an acidic catalyst of molecular sieve carried vitriol catalyzes and synthesizes a method for polyoxymethylene dimethyl ether, it is characterized in that: described method is,
In autoclave, add an acidic catalyst of paraformaldehyde, methylal, molecular sieve carried a kind of vitriol or multiple vitriol, pass into nitrogen protection, heating is reacted under magnetic stirring, has reacted rear to product centrifugation, has got supernatant liquid.
2. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: the mass ratio of methylal and paraformaldehyde is between 1:4 ~ 1:2.
3. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: the consumption of described an acidic catalyst is 0.5% ~ 5% of reactant methylal and the paraformaldehyde total mass added.
4. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: described in pass into nitrogen pressure be 1MPa ~ 2MPa.
5. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: Heating temperature is 110 DEG C ~ 130 DEG C, and the magnetic agitation time is 3h ~ 12h.
6. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: the preparation method of an acidic catalyst of described molecular sieve carried vitriol is,
Vitriol and Hydrogen Y zeolite are placed in beaker, add deionized water, then the sulfuric acid that Solute mass concentration is 5% ~ 10% is added dropwise to, room temperature is cooled to after 80 DEG C ~ 120 DEG C heated and stirred 4 ~ 6h, suction filtration, with deionized water rinsing to the liquid pH flushed out in neutral, dry 4h ~ 5h at putting into 90 DEG C ~ 110 DEG C, baking oven, cooling, obtains catalyst S O
4 2-/ HY.
7. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 6, it is characterized in that: the silica alumina ratio of described Hydrogen Y zeolite is 1:10 ~ 40.
8. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 6, it is characterized in that: described Hydrogen Y zeolite and the mass ratio of vitriol are 2:1 ~ 5:1.
9. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 6, it is characterized in that: described vitriol is Al
2(SO
4)
3, CdSO
4, CuSO
4, SrSO
4, Fe
2(SO
4)
3, MnSO
4, Ce
2(SO
4)
3, FeSO
4, CaSO
4, ZnSO
4, NiSO
4, CoSO
4, CrSO
4or MgSO
4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510557855.9A CN105237366A (en) | 2015-09-06 | 2015-09-06 | Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve |
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|---|---|---|---|
| CN201510557855.9A CN105237366A (en) | 2015-09-06 | 2015-09-06 | Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve |
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Family
ID=55035242
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398991A (en) * | 2021-05-26 | 2021-09-17 | 华东理工大学 | Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst |
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Application publication date: 20160113 |