CN1911505A - Catalyst required for coproducing N-methyl morpholine and morpholine - Google Patents
Catalyst required for coproducing N-methyl morpholine and morpholine Download PDFInfo
- Publication number
- CN1911505A CN1911505A CN 200510090149 CN200510090149A CN1911505A CN 1911505 A CN1911505 A CN 1911505A CN 200510090149 CN200510090149 CN 200510090149 CN 200510090149 A CN200510090149 A CN 200510090149A CN 1911505 A CN1911505 A CN 1911505A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- mgo
- cao
- morpholine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The catalyst for co-producing N-methyl morpholine and morpholine with materials including diglycol, liquid ammonia and monomethyl amine consists of carrier of (delta + theta)Al2O3, MgO, CaO or BaO and supported active components of Ni and Cu. Specifically, the catalyst consists of carrier in 78 wt% and active components including Ni 12 wt% and Cu 10 wt%. The preparation process of the catalyst includes soaking cloverleaf formed gamma-Al2O3 in water solution of nitrate of Mg, Ca or Ba, drying and calcining to obtain the carrier, soaking the carrier in mixed solution of nitrate of Cu and Ni, drying, drying and calcining to obtain the catalyst.
Description
Technical field
The present invention relates to a kind of coproduction N-methylmorpholine and the needed catalyst of morpholine.
Background technology
Patent CN87105893, the CN87105833 of Research Inst. of Petroleum Processing, SINOPEC disclose at Ni-Cu-Cr-Re/Al
2O
3Catalyst exists down, is raw material with diethylene glycol (DEG) (GDE) and liquefied ammonia, adopts liquid phase method fixed bed reaction technology to prepare morpholine, and its yield is 80～93%; With diethylene glycol (DEG), methyl alcohol and liquefied ammonia is raw material, and coproduction N-methylmorpholine and morpholine, the yield of its N-methylmorpholine are 66%, and the yield of morpholine is 23%.This technical method is owing to adopt liquid phase method, and reaction system generates cupric ammine complex owing to exist a large amount of water and liquefied ammonia, the Cu in the catalyst very easily to be corroded and runs off, and catalyst is short service life, thereby it applies not success.
U.S. Pat 3151113 adopts Ni-Cu-Cr catalyst and high pressure batch reactor, is raw material with diethylene glycol (DEG), fatty alcohol and liquefied ammonia, liquid phase method synthesis of alkyl morpholine.Japan Patent JP58-225078 adopts Ni-Cu-Cr-Re/ α-Al
2O
3Catalyst and high pressure batch reactor are raw material with diethylene glycol (DEG) and liquefied ammonia, the liquid phase method synthesize morpholine.All there is the shortcoming that reaction pressure is higher, product yield is lower in above-mentioned two kinds of methods.
US3709881 adopts Ni-Zr/ diatomite catalyst and fixed bed reaction mode, is the synthetic continuously N-alkyl morpholine of raw material with alkylamine and diethylene glycol (DEG).German patent DE 3337182 adopts Ni-Cu/Al
2O
3-C catalyst faces the hydrogen amination and methylates and obtain N-methylmorpholine, and yield is 92%.Shortcomings such as these two kinds of technologies exist product single, and production decision is dumb.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with diethylene glycol (DEG), liquefied ammonia, monomethyl amine, and the needed Ni-Cu/ of coproduction N-methylmorpholine and morpholine (δ+θ)-Al
2O
3-MgO, Ni-Cu/ (δ+θ)-Al
2O
3-CaO or Ni-Cu/ (δ+θ)-Al
2O
3-BaO catalyst and this method for preparing catalyst.
The objective of the invention is to realize by the following technical solutions:
A kind of coproduction N-methylmorpholine and the needed catalyst of morpholine is characterized in that: with diethylene glycol (DEG), liquefied ammonia, monomethyl amine is raw material, and this catalyst is with (the Al of δ+θ)
2O
3With any is a carrier among MgO, CaO and the BaO, load Ni and Cu two active components on it and constitute; By weight percentage, catalyst is 100 parts, and described carrier is 78%, wherein (the Al of δ+θ)
2O
375%, MgO, CaO or BaO are 3%; Described active component is 22%, and wherein Ni is 12%, and Cu is 10%.
Pore volume 0.62～the 65ml/g of above-mentioned catalyst, average pore size 14nm, pore-size distribution 100～210nm is not less than 75%, specific area 170～220m
2/ g, bulk density 0.71～0.73.
Aforesaid Preparation of catalysts method is characterized in that: with magnesium nitrate, calcium nitrate or barium nitrate aqueous solution dipping cloverleaf pattern γ-Al
2O3 carrier, drying, high-temperature calcination obtain (δ+θ)-Al
2O
3-MgO, (δ+θ)-Al
2O
3-CaO or (δ+θ)-Al
2O
3-BaO carrier; Then with the mixed solution dipping of copper nitrate and nickel nitrate, through drain, dry, calcining, just make Ni-Cu/ (δ+θ)-Al
2O
3-MgO, Ni-Cu/ (δ+θ)-Al
2O
3-CaO or Ni-Cu/ (δ+θ)-Al
2O
3-BaO catalyst; By weight percentage, catalyst is 100 parts, and described carrier is 78%, wherein (the Al of δ+θ)
2O
375%, MgO, CaO or BaO are 3%; Described active component is 22%, and wherein Ni is 12%, and Cu is 10%.
With the catalyst that the technical scheme that originally provides makes, wherein the The Nomenclature Composition and Structure of Complexes parameter is: by weight percentage, prepared catalyst is 100 parts, and carrier accounts for 78%, and wherein (δ+θ)-Al
2O
3Be 75%, MgO, CaO or BgO are 3%; And active component is 22%, and wherein Ni is 12%, and Cu is 10%.Pore volume 0.62～65ml/g, average pore size 14nm, pore-size distribution 100～210nm is not less than 75%, specific area 170～220m
2/ g, bulk density 0.71～0.73.
The used catalyst carrier MA430 cloverleaf pattern gama-alumina of the present invention is that Tianjin chemical research institute produces, its important technological parameters is: gama-alumina content 〉=96%, silica≤0.1%, sodium oxide molybdena≤0.03%, pore volume 0.73～0.75ml/g, average pore size 18nm (pore-size distribution 120～260nm is not less than 75%), specific area 250～280m
2/ g, bulk density 0.53～0.55, carrier diameter 3.2mm.)
The present invention compared with prior art has following significant technological progress and tangible good effect: catalyst serviceability provided by the invention is stable, long service life, and the catalytic activity height, anti-carbon deposition ability is strong; In the presence of this catalyst, keep and have excess ammonia in the system, can avoid the generation of byproducts such as dimethylamine and trimethylamine, reduced the unit consumption of methylamine, simplified separation process; Simultaneously can be according to the conditions of demand in market, by changing the raw material proportioning scheme of adjusting the product mix, therefore have bigger operating flexibility
The specific embodiment
Now the present invention is further described as follows in conjunction with the specific embodiment:
Example 1 (Preparation of catalysts)
Φ 3.2 cloverleaf pattern γ-Al
2O
3Carrier, drains at 70 ℃ of dippings 3～4 hours down then with 4% magnesium nitrate aqueous solution, and 120 ℃ dry 16 hours down.Then carry out high-temperature calcination, kept 4 hours after being warming up to 850 ℃ with 50 ℃/30min speed.In beaker, add the carrier of 50 grams after calcining, put into 85 ℃ of water-baths; Copper nitrate, nickel nitrate are mixed with the mixed solution that content is 118 gram copper nitrate/L, 142 gram nickel nitrate/L, put into 85 ℃ of water-baths.After treating the two temperature constant, above-mentioned mixed solution is joined in the described beaker that carrier is housed, just do not had carrier to be advisable with liquid.Flooded 4 hours, and constantly shook beaker during this period.The catalyst that will flood is pulled out and is drained then, in 120 ℃ dry 16 hours down, carry out high-temperature calcination again, kept 4 hours after being warming up to 400 ℃ with 50 ℃/30min speed, just make needed Ni-Cu/ (δ+θ)-Al
2O
3-MgO catalyst.
Example 2～9 (Application of Catalyst)
With Ni-Cu/ (δ+θ)-Al
2O
3-MgO catalyst breakage becomes 24～32 purpose particles, and weighing 10ml (about 8 grams) is filled in the reactor, and uses hydrogen reducing 8 hours under 300 ℃ of conditions, and hydrogen flowing quantity is controlled at 50ml/min.Diethylene glycol (DEG), methylamine and liquefied ammonia is added in the material-compound tank in 1: 2: 8 ratio prepares.The raw material that will prepare above with constant-flux pump adds in the blender on vaporizer top continuously then, after mixing from the hydrogen in the hydrogen gas cylinder, the vaporizer bone that enters into reactor top together gasifies, gaseous phase materials is continuously through the beds of microreactor, product enters gas-liquid separator after condenser condenses, collect the thick product of liquid phase, gas phase emptying after counterbalance valve and absorption tower absorption.Concrete operations condition and reaction result see Table 1.
The process conditions and the reaction result of 2～9 operations of table 1. example
| Instance number | Temperature ℃ | Pressure Mpa | DEG air speed h -1 | H∶DEG | DEG conversion ratio % | Morpholine yield % | NMML yield % | Total recovery % |
| 2 | 190 | 1.0 | 0.08 | 80 | 94.7 | 55.2 | 26.4 | 81.6 |
| 3 | 210 | 1.8 | 0.12 | 50 | 99.3 | 50.7 | 37.1 | 87.8 |
| 4 | 220 | 2.5 | 0.12 | 40 | 99.1 | 49.8 | 38.3 | 88.1 |
| 5 | 230 | 1.3 | 0.16 | 50 | 98.6 | 52.1 | 35.3 | 87.4 |
| 6 | 240 | 1.8 | 0.20 | 50 | 98.9 | 54.2 | 33.2 | 87.4 |
| 7 | 250 | 1.8 | 0.15 | 50 | 100 | 47.5 | 36.4 | 83.9 |
| 8 | 260 | 1.5 | 0.15 | 50 | 100 | 43.2 | 37.3 | 80.5 |
| 9 | 220 | 1.8 | 0.14 | 20 | 93.2 | 47.9 | 27.3 | 75.2 |
Illustrate:
Total recovery %=N-methyl morpholine yield %+ morpholine yield %
Example 10～15
With Ni-Cu/ (δ+θ)-Al
2O
3-MgO catalyst breakage becomes 24～32 purpose particles, and weighing 10ml (about 8 grams) is filled in the reactor, and uses hydrogen reducing 8 hours under 300 ℃ of 4 condition, and hydrogen flowing quantity is controlled at 50ml/min.Reaction pressure 1.8Mpa, reaction temperature is 220 ℃, the DEG air speed is 0.14h
-1, the mol ratio of hydrogen and diethylene glycol (DEG) is 50: 1, the mol ratio of liquefied ammonia and diethylene glycol (DEG) is 8: 1.All the other operations are with example 2～9.The process conditions and the reaction result of example 10～15 see Table 2.
The process conditions of table 2 example 10～15 and reaction result
| Instance number | Methylamine: DEG | Liquefied ammonia: DEG | DEG conversion ratio % | Morpholine conversion ratio % | Transform NMML and lead % | Total conversion % |
| 10 | 0 | 5 | 98.3 | 81.7 | 2.4 | 84.1 |
| 11 | 0 | 10 | 99.7 | 81.7 | 1.1 | 87.3 |
| 12 | 1.0 | 6 | 99.3 | 58.6 | 27.6 | 80.2 |
| 13 | 1.5 | 8 | 99.6 | 55.3 | 33.1 | 88.4 |
| 14 | 2.0 | 8 | 100 | 48.9 | 38.5 | 87.4 |
| 15 | 3.0 | 8 | 99.4 | 41.6 | 46.9 | 87.5 |
Example 16
Replace the magnesium nitrate solution of example 1 with 4% calcium nitrate solution, and prepare Ni-Cu/ (δ+θ)-Al according to the step of example 1
2O
3-CaO catalyst.Operate according to example 2, its process conditions are identical with example 14.The conversion ratio of diethylene glycol (DEG) is 99.2%, and the morpholine yield is 43.2%, and the methyl morpholine yield is 44.1%, total recovery 87.3%.
Example 17
Replace the magnesium nitrate solution of example 1 with 4% calcium nitrate solution, and prepare Ni-Cu/ (δ+θ)-Al according to the step of example 1
2O
3-BaO catalyst.Operate according to example 2, its process conditions are identical with example 14.The conversion ratio of diethylene glycol (DEG) is 99.4%, and the morpholine yield is 50.6%, and the methyl morpholine yield is 31.2%, total recovery 81.8%.
Claims (3)
1, a kind of coproduction N-methylmorpholine and the needed catalyst of morpholine, it is characterized in that: with diethylene glycol (DEG), liquefied ammonia, monomethyl amine is raw material, this catalyst is with (the Al of δ+θ)
2O
3With any is a carrier among MgO, CaO and the BaO, load Ni and Cu two active components on it and constitute; By weight percentage, catalyst is 100 parts, and described carrier is 78%, wherein (the Al of δ+θ)
2O
375%, MgO, CaO or BaO are 3%; Described active component is 22%, and wherein Ni is 12%, and Cu is 10%.
2, catalyst according to claim 1 is characterized in that: the pore volume 0.62～65ml/g of this catalyst, and average pore size 14nm, pore-size distribution 100～210nm is not less than 75%, specific area 170～220m
2/ g, bulk density 0.71～0.73.
3, Preparation of catalysts method as claimed in claim 1 is characterized in that: with magnesium nitrate, calcium nitrate or barium nitrate aqueous solution dipping cloverleaf pattern γ-Al
2O3 carrier, drying, high-temperature calcination obtain (δ+θ)-Al
2O
3-MgO, (δ+θ)-Al
2O
3-CaO or (δ+θ)-Al
2O
3-BaO carrier; Then with the mixed solution dipping of copper nitrate and nickel nitrate, through drain, dry, calcining, just make Ni-Cu/ (δ+θ)-Al
2O
3-MgO, Ni-Cu/ (δ+θ)-Al
2O
3-CaO or Ni-Cu/ (δ+θ)-Al
2O
3-BaO catalyst; By weight percentage, catalyst is 100 parts, and described carrier is 78%, wherein (the Al of δ+θ)
2O
375%, MgO, CaO or BaO are 3%; Described active component is 22%, and wherein Ni is 12%, and Cu is 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100901494A CN100548477C (en) | 2005-08-11 | 2005-08-11 | A kind of coproduction N-methylmorpholine and the needed catalyst of morpholine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100901494A CN100548477C (en) | 2005-08-11 | 2005-08-11 | A kind of coproduction N-methylmorpholine and the needed catalyst of morpholine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1911505A true CN1911505A (en) | 2007-02-14 |
| CN100548477C CN100548477C (en) | 2009-10-14 |
Family
ID=37720656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100901494A Active CN100548477C (en) | 2005-08-11 | 2005-08-11 | A kind of coproduction N-methylmorpholine and the needed catalyst of morpholine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100548477C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416325A (en) * | 2011-10-25 | 2012-04-18 | 中国海洋石油总公司 | Preparation method of isobutyl ketone synthesis catalyst |
| CN114618390A (en) * | 2020-12-08 | 2022-06-14 | 江苏万盛大伟化学有限公司 | Fixed bed reactor for producing N-methylmorpholine by continuous method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58225078A (en) | 1982-06-25 | 1983-12-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for preparation of morpholine |
| DE19709488A1 (en) * | 1997-03-07 | 1998-09-10 | Basf Ag | Process for the N-alkylation of amines |
-
2005
- 2005-08-11 CN CNB2005100901494A patent/CN100548477C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416325A (en) * | 2011-10-25 | 2012-04-18 | 中国海洋石油总公司 | Preparation method of isobutyl ketone synthesis catalyst |
| CN102416325B (en) * | 2011-10-25 | 2014-03-05 | 中国海洋石油总公司 | Preparation method of isobutyl ketone synthesis catalyst |
| CN114618390A (en) * | 2020-12-08 | 2022-06-14 | 江苏万盛大伟化学有限公司 | Fixed bed reactor for producing N-methylmorpholine by continuous method |
| CN114618390B (en) * | 2020-12-08 | 2024-02-20 | 江苏万盛大伟化学有限公司 | Fixed bed reactor for producing N-methylmorpholine by continuous method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100548477C (en) | 2009-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101851542B1 (en) | A hydrocracking catalyst, process for preparing the same and use thereof | |
| CN102432565B (en) | Method for preparing 2-hydroxyethylpiperazine | |
| CN107185594B (en) | Preparation method of Ni-Zn-K-Ru/MOF catalyst | |
| CN108623436B (en) | Method for converting cellulose into bioethanol by one-pot method | |
| WO2016152888A1 (en) | Catalyst for hydrogenating aromatic hydrocarbons, and hydrogenation treatment method in which same is used | |
| CN101214455A (en) | Preparation method of supported nano hydrogenation catalyst | |
| CN114471448A (en) | Benzene refining desulfurization adsorbent and preparation method thereof | |
| CN1911505A (en) | Catalyst required for coproducing N-methyl morpholine and morpholine | |
| CN102441426B (en) | Cycloalkane hydroconversion catalyst and preparation method and application thereof | |
| CN103372459A (en) | Cyclane hydro-conversion catalyst, preparation method and applications | |
| CN107376936A (en) | A kind of platinum cobalt/attapulgite catalyst and its preparation method and application | |
| CN111905753A (en) | Catalyst for catalyzing amine salt conversion, preparation method of catalyst and preparation method of DAM | |
| CN111686793B (en) | Composite catalyst and preparation and application thereof | |
| CN1911919A (en) | Method of coproducing N-methyl morpholine and morpholine | |
| CN1743068A (en) | Copper-boron catalyst for preparing butylene oxide by hydrogenating dimethyl maleate and preparing method | |
| CN1186117C (en) | Low cost sulfur transformation resistant deoxidizing agent | |
| CN113578372A (en) | Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof | |
| CN101058073A (en) | Method for preparing nickel nanometer line network particle catalyst | |
| CN114100616B (en) | Hydrocarbon steam conversion catalyst and its preparation method | |
| CN114073945B (en) | Composite alumina catalyst and preparation method and application thereof | |
| CN116060056B (en) | Residual oil hydrodemetallization catalyst and preparation method and application thereof | |
| CN114539191B (en) | Method for preparing GBL by maleic anhydride hydrogenation and 1, 4-butanediol dehydrogenation coupling method | |
| CN113231064B (en) | Method for synthesizing diisobutylamine, catalyst and preparation method of catalyst | |
| CN117816183A (en) | Maleic anhydride hydrogenation catalyst and preparation method thereof | |
| Liu et al. | Synthesis of nanofibrous ZnAl2O4 for hydrogenation of CO2 to formate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |