CN101992114B - Catalyst for preparing N-formyl morpholine - Google Patents
Catalyst for preparing N-formyl morpholine Download PDFInfo
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- CN101992114B CN101992114B CN2009100657239A CN200910065723A CN101992114B CN 101992114 B CN101992114 B CN 101992114B CN 2009100657239 A CN2009100657239 A CN 2009100657239A CN 200910065723 A CN200910065723 A CN 200910065723A CN 101992114 B CN101992114 B CN 101992114B
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Abstract
The invention provides a catalyst for preparing N-formyl morpholine, comprising the following components in content: (A) 20-85 percent of molecular sieve; (B) 1-79 percent of carrier; and (C) 1-14 percent of binder, wherein the molecular sieve is Y-type molecular sieve or ZSM-5 molecular sieve; in the Y-type molecular sieve, the ratio of SiO2 to Al2O3 is 1-5; the ZSM-5 molecular sieve is a hydrogenous molecular sieve or a molecular sieve modified by modification elements including phosphorus and sulphur, wherein the content of the modification elements of phosphorus and sulphur is 0.1-5wt%; the carrier is Al2O3; and the binder is one or a mixture of pseudo-boehmite or hydroxyl aluminum chloride sol, silica-aluminum sol and aluminium phosphate sol. The ratio of SiO2 to Al2O3 for the modified ZSM-5 molecular sieve is 20-500, and a restricted index is 1-2. By using the catalyst of the invention, the yield and the purity of the product are high, the problem on the separation of the catalyst and a reactant does not exist, and product quality is improved beneficially.
Description
Technical field
The present invention relates to a kind of catalyzer of the N-of preparation N-formyl morpholine N-, relate to a kind of catalyzer of carrying the N-N-formyl morpholine N-of dense extractant and the agent of synthetic gas acid gas removal as aromatic device extractant, methyl ethyl ketone plant butylene specifically.
Background technology
The N-N-formyl morpholine N-is that the good extraction solvent and the methyl ethyl ketone plant butylene of aromatic device carried dense extraction solvent.And N-N-formyl morpholine N-and composition thereof is good Sweet natural gas and the agent of synthetic gas acid gas removal, is used for the external Morphysorb novel process of exploitation in recent years.The synthesis technique of N-N-formyl morpholine N-mainly contains formic acid method (CN1345723, CN1356324 and 1482121), carbon monoxide oxo synthesis and methyl-formiate method.
CN1132825C provides a kind of formic acid method synthetic route; Catalyst system therefor is sulfuric acid, hydrochloric acid, phosphoric acid, zirconium sulfate, ion exchange resin etc.; Reaction system acidity is very strong, and seriously corroded needs to adopt expensive corrosion resistant apparatus; There is simultaneously waste water to produce in the production process, is prone to residual formic acid in the product and has corrodibility.
Carbon monoxide carbon back synthesis method adopts CO to make acylating agent, and abundant raw material is cheap, but needs to adopt expensive catalysts and under high temperature, highly compressed condition, could realize, complex process is high to equipment requirements, invests bigger.
CN200510058892.1 provides the method for the synthetic N-N-formyl morpholine N-of a kind of methyl-formiate method; Adopt transesterification catalyst, like sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide, Dibutyltin oxide, dioctyl tin oxide, titanic acid ester or their compound.
The process characteristic of methyl-formiate method does, the process side reaction is few, the little and anhydrous generation of corrosion, and technology is simple, and morpholine and methyl-formiate transformation efficiency, product yield and quality are all than higher, and especially free acid content is much smaller than the formic acid method.
It is homogeneous catalyst that these several kinds of compound methods exist catalyzer, and catalyzer and product separation be difficulty, and spent acid is handled difficulty; Reaction times is longer, and side reaction is more, makes the numerous and diverse poor product quality of post-reaction treatment; And produce a large amount of waste liquids, cause problems such as environmental pollution.
Summary of the invention
The present invention is a homogeneous catalyst for the catalyzer that solves the prior art existence, and catalyzer and product separation be difficulty, and spent acid is handled difficulty; Reaction times is longer; Side reaction is more, makes the numerous and diverse poor product quality of post-reaction treatment, and produces a large amount of waste liquids; Cause technical problems such as environmental pollution, a kind of catalyzer of the N-of preparation N-formyl morpholine N-is provided.This catalyzer is a solid acid catalyst.
In order to address the above problem, the catalyzer of preparation N-N-formyl morpholine N-provided by the invention is made up of following compositions and content:
(A) molecular sieve 20～85%;
(B) carrier 1%～79%;
(C) sticker 1%～14%;
Above-mentioned percentage ratio is weight percentage, in total catalyst weight;
Said molecular sieve is Y zeolite or ZSM-5 molecular sieve; Y zeolite is HY, REY, REHY, USY or REUSY; The ZSM-5 molecular sieve is a Hydrogen or through the molecular sieve of modifying element modification, with modifying element phosphorus, sulphur modification, the content of modifying element phosphorus, sulphur is 0.1～5 weight %; Said carrier is Al2O3, can get from its precursor pseudo-boehmite; Said sticker is pseudo-boehmite or aluminium chlorohydroxide colloidal sol, silica-alumina gel, phosphagel phosphaljel colloidal sol or their mixture.
The used sticker of the present invention is preferably pseudo-boehmite, and described molecular sieve content is preferably 35～85 weight %, and vector contg is preferably 10～65 weight %.
The present invention is used for the ZSM-5 molecular sieve of modification, is commercially available ZSM-5 molecular sieve, and its SiO2/Al2O3 ratio is 20～500, is preferably 25～200, and restricted index is 1～2.The Y zeolite that the present invention uses is commercially available HY, REY, REHY, USY or REUSY molecular sieve, and its SiO2/Al2O3 ratio is 1～5.
The invention provides the method for the catalyzer of preparation N-N-formyl morpholine N-, this method comprises according to the following steps:
(1), evenly grinds with commercially available Hydrogen ZSM-5 molecular sieve or through the ZSM-5 of modification molecular sieve or HY type molecular sieve, carrier and sticker proportional mixing;
(2) with nitric acid be mixed with weight percent be 2～4% drips of solution add mix in the ground material pinch after; Use banded extruder and suitable mold (can be trifolium-shaped, stripe shape, Raschig ring type etc.) extruded moulding or punching press to use the stamping machine impact briquetting then, 100～150 ℃ of oven dry down;
(3) material after the oven dry is preferably 490～550 ℃ of roastings 3～5 hours at 450～560 ℃.
(4) bar shaped catalyst that also can prepare with 80% phosphoric acid and an amount of zero(ppm) water dipping again flooded 4～12 hours, oven dry then, and under 500～550 ℃, roasting 4 hours makes catalyzer again.
Through above-mentioned preparation method, it is a kind of solid acid catalyst that the present invention obtains catalyzer, can replace homogeneous catalysts such as sulfuric acid, hydrochloric acid, sodium methylate, potassium methylate; Because solid acid catalyst belongs to heterogeneous catalyst, does not have the separation problem of catalyzer and reaction product, adopts higher temperature of reaction simultaneously; Reaction times is shortened greatly; Owing to do not contain liquid acid in the solid acid catalyst, therefore do not exist yet and separate the problem that spent acid is handled, help improving the quality of products.The notion of so-called solid acid (solid acid) is from hydrocarbon polymer and mineral acid; For example sulfuric acid or hydrofluoric acid etc. are understood some reactions of catalysis like cracking (cracking), and some solid catalyst; Like aluminum oxide or zeolite similar effect is arranged also, therefore be called solid acid.
Through embodiment the present invention is done further elaboration below, but these embodiment do not limit the scope of the invention.
Embodiment
Embodiment 1～12nd, Preparation of catalysts example of the present invention, and embodiment 13 is evaluation Example of catalyzer of the present invention.
Embodiment 1
Get commercially available silica alumina ratio and be 60 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 240 grams (butt), get commercially available pseudo-boehmite 100 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 120 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.Make catalyst A.
Embodiment 2
Get commercially available silica alumina ratio and be 34 HZSM-5 molecular sieve 240 grams (the Tianjin good fortune is given birth to the dye house and produced) (butt), get commercially available pseudo-boehmite 100 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm bar type die extrusion then, descend to dry 4 hours at 120 ℃; Material after the oven dry was 550 ℃ of roastings 4 hours.Make catalyst B.
Embodiment 3
Get commercially available silica alumina ratio and be 100 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 240 grams (butt), get commercially available pseudo-boehmite 100 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 115 ℃; Material after the oven dry was 545 ℃ of roastings 5 hours.Make catalyzer C.
Embodiment 4
Get commercially available silica alumina ratio and be 34 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 240 grams (butt), get commercially available pseudo-boehmite 100 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 115 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 0 gram and an amount of zero(ppm) water dipping again 9 hours is dried then, and under 540 ℃, roasting 4 hours makes catalyzer D again, and wherein molecular sieve content is 78%, and P content is 2%.
Embodiment 5
Get commercially available silica alumina ratio and be 100 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 240 grams (butt), get commercially available pseudo-boehmite 100 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 120 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 0 gram and an amount of zero(ppm) water dipping again 12 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer E again, and wherein molecular sieve content is 78%, and P content is 2%.
Embodiment 6
Get commercially available silica alumina ratio and be 100 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 210 grams (butt), get commercially available pseudo-boehmite 128 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 110 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 12 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer F again, and wherein molecular sieve content is 70%, and P content is 3%.
Embodiment 7
Get commercially available HY molecular sieve (CNPC's Lanzhou catalyst plant is produced) 210 grams (butt), get commercially available pseudo-boehmite 128 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 130 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 10 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer G again, and wherein molecular sieve content is 70%, and P content is 3%.
Embodiment 8
Get commercially available REUSY molecular sieve (CNPC's Lanzhou catalyst plant is produced) 210 grams (butt), get commercially available pseudo-boehmite 128 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 118 ℃; Material after the oven dry was 550 ℃ of roastings 3 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 8 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer H again, and wherein molecular sieve content is 70%, and P content is 3%.
Embodiment 9
Get commercially available silica alumina ratio and be 34 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 180 grams (butt), get commercially available pseudo-boehmite 171 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 120 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 9 hours is dried then, and under 530 ℃, roasting 4 hours makes catalyst I again.Wherein molecular sieve content is 60%, and P content is 3%.
Embodiment 10
Get commercially available silica alumina ratio and be 34 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 225 grams (butt), get commercially available pseudo-boehmite 107 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 130 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 12 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer J again.Wherein molecular sieve content is 75%, and P content is 3%.
Embodiment 11
Get commercially available silica alumina ratio and be 34 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 150 grams (butt), get commercially available pseudo-boehmite 214.5 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use banded extruder and diameter to be 2.0mm trifolium-shaped mould extrusion then, descend to dry 4 hours at 120 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The bar shaped catalyst of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 12 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer K again.Wherein molecular sieve content is 50%, and P content is 3%.
Embodiment 12
Get commercially available silica alumina ratio and be 34 HZSM-5 molecular sieve (the Tianjin good fortune is given birth to the dye house and produced) 150 grams (butt), get commercially available pseudo-boehmite 214.5 grams, organic extrusion aid 13 grams mix the HNO with 68%
3Solution 9ml adds in the 120 gram zero(ppm) water, mix pinch after, use impact molding machine and outside diameter to be 6.0mm interior diameter 3.0mm Raschig ring mould molding then, descend to dry 4 hours at 120 ℃; Material after the oven dry was 550 ℃ of roastings 5 hours.The catalyzer of having prepared with 80% phosphatase 11 5.2 gram and an amount of zero(ppm) water dipping again 10 hours is dried then, and under 550 ℃, roasting 4 hours makes catalyzer L again.Wherein molecular sieve content is 50%, and P content is 3%.
Embodiment 13
Evaluation method: the present invention is a raw material with formic acid and morpholine, adds catalyzer of the present invention, and in fixed-bed reactor or the flow reactor internal reaction, reaction product obtains product N-N-formyl morpholine N-through continuous separation technology.
Reaction formula is to be C
4H
9NO+HCOOH=C
4H
8NOCOH+H
2O
Concrete reaction conditions is following:
(1) mol ratio of morpholine and formic acid is 1.5～0.7, is preferably 1.3～0.8.
(2) temperature of reaction is 50～200 ℃, is preferably in 70～170 ℃.
(3) be reflected under the normal pressure carry out, mass space velocity is: 0.1～10.0h
-1, be preferably in 0.2～5h
-1
Implementation result of the present invention is seen table 1.
The implementation result of table 1 various catalyzer of the present invention
| Morpholine transformation efficiency (%) | Yield (%) | Product purity (%) | |
| Catalyst A | 94.5 | 98.2 | 99.8 |
| Catalyst B | 99.8 | 98.5 | 99.7 |
| Catalyzer C | 93.1 | 98.0 | 99.9 |
| Catalyzer D | 99.5 | 99.6 | 99.9 |
| Catalyzer E | 99.0 | 97.5 | 99.9 |
| Catalyzer F | 96.5 | 98.5 | 99.9 |
| Catalyzer G | 99.0 | 99.0 | 99.9 |
| Catalyzer J | 93.7 | 97.8 | 99.8 |
| Catalyzer K | 95.1 | 98.5 | 99.7 |
| Catalyst I | 96.8 | 97.5 | 99.7 |
| Catalyzer H | 99.4 | 98.7 | 99.9 |
| Catalyzer L | 99.5 | 98.2 | 99.4 |
Can be known by table 1, use catalyzer of the present invention, the yield of product and purity are all very high, do not have the separation problem of catalyzer and reaction product, help improving the quality of products.
Claims (4)
1. catalyzer for preparing the N-N-formyl morpholine N-is characterized in that being made up of following compositions and content:
(A) molecular sieve 20%～85%;
(B) carrier 1%～79%;
(C) sticker 1%～14%;
Above-mentioned percentage ratio is weight percentage, in total catalyst weight;
Said molecular sieve is Y zeolite or ZSM-5 molecular sieve, and Y zeolite is HY, REY, REHY, USY or REUSY, and the ZSM-5 molecular sieve is a hydrogen type molecular sieve; Said carrier is Al
2O
3, get from its precursor pseudo-boehmite; Said sticker is pseudo-boehmite or aluminium chlorohydroxide colloidal sol, silica-alumina gel, phosphagel phosphaljel colloidal sol or their mixture.
2. catalyzer according to claim 1 is characterized in that said sticker is a pseudo-boehmite.
3. according to described any catalyzer of claim 1～2, it is characterized in that the SiO of described ZSM-5 molecular sieve
2/ Al
2O
3Than being 20～500, restricted index is 1～2, the SiO of described Y zeolite
2/ Al
2O
3Than being 1～5.
4. catalyzer according to claim 3 is characterized in that the SiO of described ZSM-5 molecular sieve
2/ Al
2O
3Than being 25～200.
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| CN2009100657239A CN101992114B (en) | 2009-08-11 | 2009-08-11 | Catalyst for preparing N-formyl morpholine |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356324A (en) * | 2001-10-18 | 2002-07-03 | 复旦大学 | Process for preparing N-formyl morpholine |
| CN1651141A (en) * | 2004-12-01 | 2005-08-10 | 中国石油化工集团公司 | Aromatization catalyst, its preparation method and application |
| CN101062923A (en) * | 2006-04-28 | 2007-10-31 | 烟台大学 | Synthesizing N-formyl morpholine by two-step process |
| JP2007531614A (en) * | 2004-03-19 | 2007-11-08 | キャタリティック・ディスティレイション・テクノロジーズ | Ni catalyst, catalyst production method and selective hydrogenation method |
-
2009
- 2009-08-11 CN CN2009100657239A patent/CN101992114B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356324A (en) * | 2001-10-18 | 2002-07-03 | 复旦大学 | Process for preparing N-formyl morpholine |
| JP2007531614A (en) * | 2004-03-19 | 2007-11-08 | キャタリティック・ディスティレイション・テクノロジーズ | Ni catalyst, catalyst production method and selective hydrogenation method |
| CN1651141A (en) * | 2004-12-01 | 2005-08-10 | 中国石油化工集团公司 | Aromatization catalyst, its preparation method and application |
| CN101062923A (en) * | 2006-04-28 | 2007-10-31 | 烟台大学 | Synthesizing N-formyl morpholine by two-step process |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee after: Luoyang Petrochemical Engineering Corporation /SINOPEC Patentee after: China Petrochemical Group Corp. Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Co-patentee before: Luoyang Petrochemical Engineering Co., China Petrochemical Group Patentee before: China Petrochemical Group Corp. |