CN1569327A - Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof - Google Patents
Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof Download PDFInfo
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Abstract
The invention relates to diethylene glycol aminated morpholine catalyst and process. It is made up of carrier made up of unformed SiO2 produced with natural bentonite acidification, and copper, nickel, cobalt active component. Counting by catalyst weight, the active component accounts for 20-40%, nickel: copper=1:1.0-3.0, nickel: cobalt=1:0-0.3, the residue is carrier. The bentonite is added into the nitric acid liquor with liquid/solid=8, and it is acidified into the carrier under 150 minus or plus 5 deg.C; the active component nitric acid salt liquid is reacted with 15-35% natrium carbonate under temperature of 50-100deg.C, the pH value=7-8, then acquires the alkali carbonate; the carrier and alkali carbonate are squeezed into shape and acquires the catalyst, then it is reduced by hydrogen for 8-12 hours, then it is aminated.
Description
Technical field
The present invention relates to a kind of diethylene glycol (DEG) amination catalyst and technology, relate in particular to diethylene glycol (DEG) ammonification system 1,4-morpholine Catalysts and its preparation method and ammonating process.
Background technology
In organic catalysis industry, generally use hydroxy-containing compounds, as monobasic or dihydroxylic alcohols etc. in the fatty alcohol, wherein particularly corresponding fatty amine is produced in diethylene glycol (DEG) (DEG) ammonification, comprising morpholine (MOR) promptly: 1,4-morpholine catalyst.More about this respect catalyst report:
European patent EP 0,036,331 disclose the synthesize morpholine catalyst.With γ-Al
2O
3Being carrier, is active component with Ni, Co, Cr.Chinese patent ZL00105224.1 discloses C
2～8Fatty alcohol amination catalyst is a carrier with synthesizing Si-Al glue, is active component with Ni or Co or (Ni+Co).When being the catalyst activity component with Ni, Ni is 15～40%; When being active component with Co, Co is 15～30%; When (Ni+Co) is active component, be 30～40% (Ni+Co).The disclosed catalyst of Chinese patent publication number CN1031663A is with Al
2O
3(32～63%) are carrier, are active component with Ni, Cu, Cr, Ti, wherein with molar ratio computing Ni: Cu=1: 1.0～2.0, Ni: Cr=1: 0.1～0.5, Ni: Ti=1: 1.0～2.0.Diethylene glycol (DEG) conversion ratio 82.79mol%, morpholine selectivity 95.44mol%, morpholine yield 79.01%.German patent DE 3125662 discloses synthetic amination catalyst, and it is with Al
2O
3Being carrier, is active component with Ni, Cu, Co.Put down in writing 2～50%N in claims or/and Co, but equal Co component in the record in 1～3 example only in the specification.This catalysis is made by the precipitation method.Its morpholine yield is 86.06%.The problem that these catalyst exist is an active constituent metal element content height; The synthetic vectors complicated process of preparation, poor repeatability.Catalyst makes the cost height, and its activity, stability, intensity and selectivity etc. remain in weak point.
Owing in the synthetic MOR process of DEG and ammonia react, except that containing a certain amount of intermediate products diethylene glycol (DEG) ammonia (DGA), also contain ethers impurity usually in the product; as glycol monoethyl ether etc.; the boiling point of its boiling point and MOR is very approaching, increases separating difficulty, influences product and uses.
Summary of the invention
The objective of the invention is to overcome the problem that the synthetic MOR of existing DEG ammonification exists, provide a kind of active constituent content low relatively, and the catalyst strength height, active, good DEG ammonification system MOR catalyst and the technology thereof of selection performance.
The objective of the invention is to be achieved by following technical solution:
A kind of diethylene glycol (DEG) ammonification system 1,4-morpholine catalyst is characterized in that: it be by natural montmorillonite through acidifying make with unformed SiO
2Being the carrier of Main Ingredients and Appearance, is that active constituent constitutes with copper, nickel, cobalt; With the catalyst weight is benchmark, and described active constituent accounts for 20～40% of catalyst weight, and wherein copper, cobalt consumption are respectively nickel with its ratio with the nickel mole: copper=1: 1.0～3.0, nickel: cobalt=1: 0～0.3, all the other are carrier.
This Preparation of catalysts method is as follows:
1. the preparation of carrier: press bentonite: 10～25% nitric acid=1: 8, under stirring bentonite is added in the salpeter solution, be warming up to 100～110 ℃, acidification 8～12 hours, material is made carrier through wet concentration, filtration, washing.
2. with each active constituent nitrate of requirement, be dissolved in certain water gaging, again with a certain amount of 15～35% Na
2CO
3In 50～100 ℃, PH=7～8 time are precipitated, and sediment after filtration, washing makes subcarbonate.
3. the carrier of the requirement that will 1. prepare and the 2. active constituent subcarbonate of requirement of preparation, through mediate, extruded moulding, successively in 60 ℃, 120 ℃ respectively after dry 2 hours, 4 hours, again in 350～550 ℃ of roastings 4 hours.
The above-mentioned catalyst that makes is used for diethylene glycol (DEG) ammonification preparation 1, the method of 4-morpholine, this ammonification is carried out in fixed bed reactors, it is characterized in that catalyst packs in the reactor, after handling 8～12 hours, 280～380 ℃ of logical hydrogen reductions drop to reaction temperature with the qualified back of nitrogen replacement, diethylene glycol (DEG) and liquefied ammonia vaporization back is being faced under the hydrogen state in 210～280 ℃ of temperature, and pressure is 1～2Mpa, and alcohol is with 0.16～0.2h
-1Air speed (volume), by the catalyst that filling makes, charge ratio is: diethylene glycol (DEG): ammonia: hydrogen=1: 8～16: 20～50 (mol ratio).
Above-mentioned catalysqt deactivation adopts the regeneration of oxidizing roasting method, flows down under 200 ℃, 300 ℃, 400 ℃ respectively at air, and regenerating re-uses after 2 hours, 4 hours, 8 hours.
Carrier provided by the invention is measured its chemical composition through chemical analysis, and it is as follows that mercury injection method is measured its physical property:
Chemical composition: SiO
2: 85～95%
Al
2O
3：2～9％
Other: 3～6%
Physical property: pore volume: 0.5～0.8ml/g
Specific area: 100～150m
2/ g
Catalyst provided by the invention can be widely used in all kinds of aminating reactions, especially is suitable for producing MOR with DEG for the raw material ammonification.Compare with existing technologies and to have following remarkable result.
1. catalyst activity height, to make the yield of MOR be 89.43～94.14% thereby can make the DEG conversion ratio reach 99.10%～99.60%.
2. have mechanical strength and good stable preferably, move more than 12 months continuously, do not find the catalyst granules breakage through industrialization.
3. this catalyst preparation process is simple, good reproducibility, and raw material is easy to get, also renewable use behind the catalysqt deactivation, long service life has reduced the production cost of Preparation of catalysts cost and MOR significantly.
The specific embodiment
Now in conjunction with the embodiments the present invention is further described as follows:
Embodiment 1
1. prepare carrier: with the concentration for preparing is that 12% (quality) salpeter solution adds in the acid treatment still, and, under agitation add the raw material bentonite by 1: 8 solid-to-liquid ratio, be warming up to 105 ± 5 ℃, acidification reaction made required carrier through wet concentration, filtration and washing after reducing to room temperature in 12 hours.
2. prepare the active constituent subcarbonate: by the proportioning of the required active constituent of catalyst in the technical solution of the present invention, take by weighing 150g nitrate trihydrate copper, 112.5g six water nickel nitrates, 30g cobalt nitrate hexahydrate, be dissolved in the 500ml water, be mixed with the corresponding nitrate mixed solution of above-mentioned active component, with 23% (quality) sodium carbonate 600ml, precipitate 55 ± 5 ℃ of precipitation temperatures according to a conventional method, pH value 7～8, precipitation material are after filtration, washing makes the subcarbonate of required active constituent.
3. prepare catalyst: take by weighing by catalyst composition proportioning and 1. make carrier 100g, 2. the described subcarbonate 61.7g that makes, with its mixing, through kneading, extrusion, moulding, 60 ℃ dry 2 hours down, and under 120 ℃ again after dry 4 hours, with it in 450 ℃ of roastings 4 hours, make catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: estimate above-mentioned preparation catalyst with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 34g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, beginning to heat up slowly feeds hydrogen when reaching 280 ℃, reduction is 8 hours under 300 ℃ of hydrogen streams.System is adjusted to the required process conditions of ammonification, 210 ℃ of control reaction temperatures, reaction pressure 1.7Mpa, diethylene glycol (DEG) volume space velocity 0.18h
-1, in mole DEG: ammonia: hydrogen=1: 8: 40.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, it the results are shown in Table 2.
Embodiment 2
1. prepare carrier: with the concentration for preparing is that 10% (quality) salpeter solution adds in the acid treatment still, and, under agitation add the raw material bentonite by 1: 8 solid-to-liquid ratio, be warming up to 105 ± 5 ℃, acidification reaction made required carrier through wet concentration, filtration and washing after reducing to room temperature in 12 hours.
2. prepare the active constituent subcarbonate: by the proportioning of the required active constituent of catalyst in the technical solution of the present invention, take by weighing 293g nitrate trihydrate copper, 300g six water nickel nitrates, 45.5g cobalt nitrate hexahydrate, be dissolved in the 1420ml water, be mixed with the corresponding nitrate mixed solution of above-mentioned active component, with 30% (quality) sodium carbonate 1200ml, precipitate 65 ± 5 ℃ of precipitation temperatures according to a conventional method, pH value 7～8, precipitation material are after filtration, washing makes the subcarbonate of required active constituent.
3. prepare catalyst: take by weighing by catalyst composition proportioning and 1. make carrier 100g, 2. the described subcarbonate 61.7g that makes, with its mixing, through kneading, extrusion, moulding, 60 ℃ dry 2 hours down, and under 120 ℃ again after dry 4 hours, with it in 450 ℃ of roastings 4 hours, make catalyst prod, its main physical index sees Table 1.
4. evaluating catalyst: estimate above-mentioned preparation catalyst with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 35.2g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, beginning to heat up slowly feeds hydrogen when reaching 280 ℃, reduction is 8 hours under 300 ℃ of hydrogen streams.System is adjusted to the required process conditions of ammonification, 230 ℃ of control reaction temperatures, reaction pressure 1.7Mpa, diethylene glycol (DEG) volume space velocity 0.16h
-1, in mole DEG: ammonia: hydrogen=1: 16: 50.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, its result all sees Table 2.
Embodiment 3
1. prepare carrier: with the concentration for preparing is that 25% (quality) salpeter solution adds in the acid treatment still, and by 1: 8 solid-to-liquid ratio, under agitation add the raw material bentonite, be warming up to 105 ± 5 ℃, after acidification reaction under this temperature was reduced to room temperature in 8 hours, make required carrier through wet concentration, filtration and washing.
2. prepare the active constituent subcarbonate: by the proportioning of the required active constituent of catalyst in the technical solution of the present invention, take by weighing 228g nitrate trihydrate copper, 171g six water nickel nitrates, be dissolved in the 800ml water, be mixed with the corresponding nitrate mixed solution of above-mentioned active component, with 25% (quality) sodium carbonate 600ml, precipitate according to a conventional method, 75 ± 5 ℃ of precipitation temperatures, pH value 7～8, precipitation material are after filtration, washing makes the subcarbonate of required active constituent.
3. prepare catalyst: take by weighing by catalyst composition proportioning and 1. make carrier 100g, 2. the described subcarbonate 61.7g that makes, with its mixing, through kneading, extrusion, moulding, 60 ℃ dry 2 hours down, and under 120 ℃ again after dry 4 hours, with it in 450 ℃ of roastings 4 hours, make catalyst prod, its main physical index sees Table 2.
4. evaluating catalyst: estimate the above-mentioned catalyst that makes with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 32.9g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, begin to heat up and slowly feed hydrogen when reaching 250 ℃, reduction is 8 hours under 280 ℃ of hydrogen streams, and system is adjusted to the required process conditions of ammonification, 230 ℃ of control reaction temperatures, reaction pressure 1.2Mpa, diethylene glycol (DEG) volume space velocity 0.18h
-1, in mole DEG: ammonia: hydrogen=1: 12: 30.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, its result all sees Table 2.
Embodiment 4
1. prepare carrier: with the concentration for preparing is that 25% (quality) salpeter solution adds in the acid treatment still, and by 1: 8 solid-to-liquid ratio, under agitation add the raw material bentonite, be warming up to 105 ± 5 ℃, after acidification reaction under this temperature was reduced to room temperature after 8 hours, make required carrier through wet concentration, filtration and washing.
2. prepare the active constituent subcarbonate: by the proportioning of the required active constituent of catalyst in the technical solution of the present invention, take by weighing 180g nitrate trihydrate copper, 113g six water nickel nitrates, 17.1g cobalt nitrate hexahydrate, be dissolved in the 500ml water, be mixed with the corresponding nitrate mixed solution of above-mentioned active component, with 20% (quality) sodium carbonate 400ml, precipitate 85 ± 5 ℃ of precipitation temperatures according to a conventional method, pH value 7～8, precipitation material are after filtration, washing makes the subcarbonate of required active constituent.
3. prepare catalyst: by catalyst form proportioning take by weighing 1. make carrier 100g with by the 2. described subcarbonate 63.29g that makes, with its mixing, through kneading, extrusion, moulding, drying is 2 hours under 60 ℃, and after under 120 ℃ dry again 4 hours, it in 400 ℃ of roastings 4 hours, is made catalyst prod, and its main physical index sees Table 1.
4. evaluating catalyst: estimate above-mentioned preparation catalyst with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 34g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, beginning to heat up slowly feeds hydrogen when reaching 280 ℃, reduction is 8 hours under 300 ℃ of hydrogen streams.System is adjusted to the required process conditions of ammonification, 210 ℃ of control reaction temperatures, reaction pressure 2.0Mpa, diethylene glycol (DEG) volume space velocity 0.18h
-1, in mole DEG: ammonia: hydrogen=1: 8: 40.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, its result all sees Table 2.
Embodiment 5
1. prepare carrier: with the concentration for preparing is that 25% (quality) salpeter solution adds in the acid treatment still, and by 1: 8 solid-to-liquid ratio, under agitation add the raw material bentonite, be warming up to 105 ± 5 ℃, after acidification reaction under this temperature was reduced to room temperature after 8 hours, make required carrier through wet concentration, filtration and washing.
2. prepare the active constituent subcarbonate: by the proportioning of the required active constituent of catalyst in the technical solution of the present invention, take by weighing 190g nitrate trihydrate copper, 75g six water nickel nitrates, 3g cobalt nitrate hexahydrate, be dissolved in the 500ml water, be mixed with the corresponding nitrate mixed solution of above-mentioned active component, with 25% (quality) sodium carbonate 450ml, precipitate 95 ± 5 ℃ of precipitation temperatures according to a conventional method, pH value 7～8, precipitation material are after filtration, washing makes the subcarbonate of required active constituent.
3. prepare catalyst: form proportioning by catalyst and take by weighing the carrier 100g that 1. makes, 2. the described subcarbonate that makes with 58.8g, after its mixing, through kneading, extrusion, moulding, 60 ℃ dry 2 hours down, and under 120 ℃ again after dry 4 hours, with it in 500 ℃ of roastings 4 hours, make catalyst prod, its main physical index sees Table 1 appropriate section.
4. evaluating catalyst: estimate above-mentioned preparation catalyst with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 34g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, beginning to heat up slowly feeds hydrogen when reaching 280 ℃, reduction is 8 hours under 300 ℃ of hydrogen streams.System is adjusted to the required process conditions of ammonification, 210 ℃ of control reaction temperatures, reaction pressure 1.7Mpa, diethylene glycol (DEG) volume space velocity 0.18h
-1, in mole DEG: ammonia: hydrogen=1: 8: 40.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, its result all sees Table 2 appropriate sections.
Embodiment 6
1. Preparation of Catalyst carrier: with the concentration for preparing is that 23% (quality) salpeter solution adds in the acid treatment still, and, under agitation add the raw material bentonite by 1: 8 solid-to-liquid ratio, be warming up to 105 ± 5 ℃, behind the acidification reaction 10 hours, make required carrier through washing, filtration and washing.
2. prepare the active constituent subcarbonate: by the proportioning of the required active constituent of catalyst in the technical solution of the present invention, take by weighing 425g nitrate trihydrate copper, 117g six water nickel nitrates, 2.8g cobalt nitrate hexahydrate, be dissolved in the 800ml water, be mixed with the corresponding nitrate mixed solution of above-mentioned active component, with 20% (quality) sodium carbonate 600ml, precipitate 55 ± 5 ℃ of precipitation temperatures according to a conventional method, pH value 7～8, precipitation material are after filtration, washing makes the subcarbonate of required active constituent.
3. prepare catalyst: take by weighing by catalyst composition proportioning and 1. make carrier 100g, 2. the described subcarbonate 61.7g that makes, after its mixing, through kneading, extrusion, moulding, 60 ℃ dry 2 hours down, and under 120 ℃ again after dry 4 hours, with it in 450 ℃ of roastings 4 hours, make catalyst prod, its main physical index sees Table 1 appropriate section.
4. evaluating catalyst: estimate above-mentioned preparation catalyst with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 33.5g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, beginning to heat up slowly feeds hydrogen when reaching 280 ℃, reduction is 8 hours under 300 ℃ of hydrogen streams.System is adjusted to the required process conditions of ammonification, 230 ℃ of control reaction temperatures, reaction pressure 1.7Mpa, diethylene glycol (DEG) volume space velocity 2.0h
-1, in mole DEG: ammonia: hydrogen=1: 8: 40.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, its result all sees Table 2 appropriate sections.
Comparative Examples 1:
Method by USP4014933 prepares catalyst: take by weighing 20 grams, six water nickel nitrates, 6.3 gram nitrate trihydrate copper and 20 gram cobalt nitrate hexahydrates, be mixed with the aqueous solution with 150ml water; Add the 28g aluminium oxide, add 21 gram sodium carbonate again, through sedimentation and filtration, separation, wash to PH=8,120 ℃ of dryings, 350 ℃ of roastings 4 hours, moulding makes catalyst.
Above-mentioned catalyst is carried out activity rating by the embodiment of the invention 1 method: the catalyst of estimating above-mentioned preparation with the DEG ammoniation process, take by weighing in catalyst 50ml (heavy 34g) the 100ml fixed bed reactors of packing into of 3. preparation, at first carrying out catalyst reduction handles: after using the nitrogen replacement system qualified, beginning to heat up slowly feeds hydrogen when reaching 280 ℃, reduction is 8 hours under 300 ℃ of hydrogen streams.System is adjusted to the required process conditions of ammonification, 210 ℃ of control reaction temperatures, reaction pressure 1.7Mpa, diethylene glycol (DEG) volume space velocity 0.18h
-1, in mole DEG: ammonia: hydrogen=1: 8: 40.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, gets the thick product of MOR, with the thick product content of programmed temperature chromatography analysis from reactor lower part, calculate DEG conversion ratio, MOR selectivity, MOR yield, it the results are shown in Table 3.
Comparative example 2 (pressing DE3125662 example 1 preparation catalyst)
Take by weighing copper nitrate 174 grams, nickel nitrate 52.3 grams, aluminum nitrate 179g is dissolved in the 763ml water, be mixed with solution, take by weighing natrium carbonicum calcinatum 213g, be dissolved in the 1000ml water and be made into the aqueous solution, two kinds of solution are heated to 80 ℃, joined in the stillpot in 2 hours, pH value stably remains on 7～8.Sediment after filtration, washing, up to no nitrate anion, extruded moulding, in 110 ℃ of dryings 6 hours, 600 ℃ of roastings 4 hours made sample catalyst.
Carry out activity rating by the embodiment of the invention 1 method, get the 50ml catalyst fixed bed reactors of packing into, with the N2 exchange system qualified after, be warming up to 280 ℃, and feed hydrogen with 600ml/ minute, 300 ℃ of reduction 8 hours.Reduction transfers to the technological requirement condition with system, 210 ℃ of temperature, pressure 1.7Mpa, diethylene glycol (DEG) liquid air speed 0.18h after finishing
-1The time, alcohol: ammonia: hydrogen=1: 8: 40 mol ratio, thick product after the condensation gas-liquid separation, sample analysis, it the results are shown in Table 3.
Embodiment 7
To use 2000 hours amination catalyst (catalyst that this fresh catalyst makes for embodiment 1) in the fixed bed ammoniation reactor, and adopted the oxidizing roasting method to regenerate, made regenerated catalyst.Regeneration condition is: earlier with after reaction system cooling, the step-down with nitrogen purge qualified after, its programming rate that heats up is 50 ℃/h, be warming up to 180 ℃ after after the blowing air oxidation, carry out roasting again.Stopped 4 hours at 200 ℃, 300 ℃ stopped 4 hours, and 400 ℃ stopped 8 hours.Reduce to 230 ℃ of reaction temperatures then, reaction pressure 1.7Mpa, diethylene glycol (DEG) volume space velocity 0.18h
-1, in mole DEG: ammonia: hydrogen=1: 8: 40.Raw material DEG, liquefied ammonia after the vaporizer vaporization by above-mentioned reactor head charging, product through condensation, separation, obtains the thick product of MOR from reactor lower part, with the thick product content of programmed temperature chromatography analysis, calculate DEG conversion ratio, MOR selectivity, MOR yield, it the results are shown in Table 4.
Table 1 catalyst rerum natura of the present invention and content thereof
| The embodiment sequence number | Specific area m2/g | Pore volume ml/g | Catalytic component content % | Ni/Cu Mol ratio | ??Ni/Co | |||
| ??Cu | ??Ni | ??Co | Carrier | |||||
| ??1 | ??156.36 | ??0.6924 | ??15.46 | ??8.47 | ??2.23 | ??67.03 | ??1∶1.7 | ??1∶0.27 |
| ??2 | ??120.53 | ??0.5641 | ??11.26 | ??8.66 | ??1.24 | ??74.09 | ??1∶1.2 | ??1∶0.13 |
| ??3 | ??130.95 | ??0.4251 | ??15.36 | ??8.68 | ??69.72 | ??1∶1.6 | ||
| ??4 | ??179.84 | ??0.7394 | ??18.69 | ??8.64 | ??1.18 | ??64.1 | ??1∶1.9 | ??1∶0.13 |
| ??5 | ??141.25 | ??0.6906 | ??19.71 | ??7.25 | ??0.12 | ??65.95 | ??1∶2.5 | ??1∶0.02 |
| ??6 | ??134.72 | ??0.5213 | ??23.06 | ??8.52 | ??0.08 | ??61.46 | ??1∶3.0 | ??1∶0.01 |
Table 2 catalyst synthesize morpholine of the present invention evaluation result
| Example | Reaction pressure MPa | Reaction temperature ℃ | DEG conversion ratio mol% | MOR selectivity mol% | MOR yield mol% | Remarks |
| ????1 | ????1.7 | ????210 | ????99.10 | ???94.81 | ????93.96 | |
| ????2 | ????1.7 | ????230 | ????99.40 | ???91.34 | ????90.79 | |
| ????3 | ????1.7 | ????230 | ????99.00 | ???90.33 | ????89.43 | |
| ????4 | ????1.7 | ????210 | ????99.20 | ???90.98 | ????90.25 | |
| ????5 | ????1.7 | ????210 | ????99.20 | ???94.90 | ????94.14 | |
| ????6 | ????1.7 | ????230 | ????99.60 | ???90.30 | ????89.94 |
Above data are stable region mean value between the stage of reaction.
Table 3 Comparative Examples evaluation result and example of the present invention 1 are relatively
| Catalyst | Pressure MPa | Temperature ℃ | DEG conversion ratio mol% | MOR selectivity mol% | MOR once through yield mol% | Remarks |
| Example 1 | ??1.7 | ??210 | ???99.10 | ???94.81 | ???93.96 | |
| Comparative Examples 1 | ??1.7 | ??210 | ???89.20 | ???94.30 | ???84.12 | |
| Comparative Examples 2 | ??1.7 | ??210 | ???89.79 | ???95.44 | ???85.70 |
Table 4 regenerated catalyst evaluation result
| Catalyst | Pressure MPa | Temperature ℃ | DEG conversion ratio mol% | MOR selectivity mol% | MOR once through yield mol% | Remarks |
| Example 1 | ??1.7 | ????210 | ???99.10 | ???94.81 | ???93.96 | |
| Example 7 (regeneration) | ??1.7 | ????230 | ???99.88 | ???93.36 | ???93.25 |
Claims (3)
1, diethylene glycol (DEG) ammonification system 1, and 4-oxinane catalyst is characterized in that: it be by natural montmorillonite through acidifying make with unformed SiO
2Being the carrier of main component, is that active constituent constitutes with copper, nickel, cobalt; With the catalyst weight is benchmark, and described active constituent accounts for 20～40% of catalyst weight, and wherein copper, cobalt consumption are respectively nickel in its ratio with the nickel mole: copper=1: 1.0～3.0, and nickel: cobalt=1: 0～0.3, all the other are carrier,
This Preparation of catalysts method is as follows:
1. press bentonite: 10～25% nitric acid=1: 8, under stirring bentonite is added in the salpeter solution, be warming up to 100～110 ℃, acidification 8～12 hours, material is made carrier through wet concentration, filtration, washing,
2. with each active constituent nitrate of requirement, be dissolved in certain water gaging, again with a certain amount of 15～35% Na
2CO
3In 50～100 ℃, PH=7～8 time are precipitated, and sediment is after filtration, washing makes subcarbonate,
3. with the 2. active constituent subcarbonate of preparation of carrier and the requirement of the 1. preparation of requirement, through mediate, extruded moulding, in 60 ℃, 120 ℃ dryings after 2 hours, 4 hours, respectively again in 350～550 ℃ of roastings 4 hours.
2, the method that is used for the diethylene glycol (DEG) ammonification according to the described catalyst of claim 1, this ammonification is carried out in fixed bed reactors, it is characterized in that catalyst packs in the reactor, after handling 8～12 hours, 280～380 ℃ of logical hydrogen reductions drop to reaction temperature with the qualified back of nitrogen replacement, diethylene glycol (DEG) and liquefied ammonia vaporization back are being faced under the hydrogen state in 210～280 ℃ of temperature, pressure is 1～2Mpa, pure volume space velocity 0.16～0.2h
-1, with the mol ratio charging be alcohol: ammonia: hydrogen=1: 8～16: 20～50, by the reactor of catalyst filling.
3, according to the described catalyst of claim 1, it is characterized in that adopting the oxidizing roasting method to regenerate behind the catalysqt deactivation, flow down under 200 ℃, 300 ℃, 400 ℃ high temperature at air respectively, regenerate and use again after 2 hours, 4 hours, 8 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410010815 CN1240474C (en) | 2004-04-23 | 2004-04-23 | Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof |
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| CN 200410010815 CN1240474C (en) | 2004-04-23 | 2004-04-23 | Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof |
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| CN1569327A true CN1569327A (en) | 2005-01-26 |
| CN1240474C CN1240474C (en) | 2006-02-08 |
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| CN 200410010815 Expired - Fee Related CN1240474C (en) | 2004-04-23 | 2004-04-23 | Preparation of 1,4-oxygen nitrogen heterocyclic hexane catalyst by ammonification of diethylene glycol and process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690895B (en) * | 2007-10-15 | 2015-09-30 | 赢创德固赛有限责任公司 | fast filtering powder catalytic mixtures |
| CN111892555A (en) * | 2020-08-12 | 2020-11-06 | 四川鸿鹏新材料有限公司 | Morpholine production system |
| CN116178306A (en) * | 2021-11-29 | 2023-05-30 | 安徽昊源化工集团有限公司 | Morpholine synthesis process |
-
2004
- 2004-04-23 CN CN 200410010815 patent/CN1240474C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690895B (en) * | 2007-10-15 | 2015-09-30 | 赢创德固赛有限责任公司 | fast filtering powder catalytic mixtures |
| CN111892555A (en) * | 2020-08-12 | 2020-11-06 | 四川鸿鹏新材料有限公司 | Morpholine production system |
| CN116178306A (en) * | 2021-11-29 | 2023-05-30 | 安徽昊源化工集团有限公司 | Morpholine synthesis process |
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| Publication number | Publication date |
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| CN1240474C (en) | 2006-02-08 |
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