CN205761055U - A kind of device of fixed bed hydrogenation refined caprolactam - Google Patents
A kind of device of fixed bed hydrogenation refined caprolactam Download PDFInfo
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- CN205761055U CN205761055U CN201620467569.3U CN201620467569U CN205761055U CN 205761055 U CN205761055 U CN 205761055U CN 201620467569 U CN201620467569 U CN 201620467569U CN 205761055 U CN205761055 U CN 205761055U
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Abstract
This utility model relates to a kind of fixed bed hydrogenation refined caprolactam device, main by feed heater, pipe-line mixer, hydrogenation dissolves stirred tank, fixed bed hydrogenation reactor, discharging surge tank, hydrogenation discharging pump composition, impure crude caprolactam water solution enters feed heater by pipeline, feed heater is connected with pipe-line mixer import, pipe-line mixer outlet is dissolved stirred tank with hydrogenation and is connected, hydrogenation dissolves stirred tank and is connected with fixed bed hydrogenation reactor, fixed bed hydrogenation reactor is connected with discharging surge tank, discharging surge tank is connected with hydrogenation discharging pump.This utility model is applied to hydrofinishing caprolactam and is not only able to remove the unsaturated impurity in caprolactam, and flow process is the easiest, and more convenient operation, catalyst consumption is low.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of hexanolactam hydrofining device, be a kind of fixed bed hydrogenation refined caprolactam device in particular.
Background technology
Caprolactam is nylon-6 synthetic fibers and the intermediate of nylon-6 engineering plastics, with terylene, acrylic at the big synthetic fibers of China referred to as three, is widely used at the aspect such as industrial, civilian, military.
Preparing process of caprolactam long flow path, production technology are more complicated, and raw materials used have benzene, phenol and toluene etc.；At present, industrialized producing technology route mainly has two classes: first kind route is with Ketohexamethylene as intermediate product, and resynthesis is cyclohexanone-oxime, and then cyclohexanone-oxime resets synthesis crude caprolactam through Bechmann, this is the most most important manufacture method, accounts for more than the 90% of caprolactam aggregated capacity；Main production process includes Raschig process (Rasching), oxammonium sulfate. (HSO) method, nitric oxide reduction method (NO), hydroxylamine assay (HPO) and amidoxime method (HAO)；Equations of The Second Kind route avoids the production link of Ketohexamethylene, relates to other intermediate or other processing steps, as used toluene route technique, hexamethylene photonitrosation technology etc..
Because raw material is different from process route, the kind of crude caprolactam impurities and amount also have difference, in addition to containing caprolactam, possibly together with a large amount of water, a small amount of ammonium sulfate and other organic and inorganic impurity, wherein common are machine impurity has volatile base, salt, aniline, ammonium acetate, phenol, alkyl amine, Nitrobenzol, different fine base benzene, Ketohexamethylene, cyclohexanone-oxime, aminocaproic acid and other amide-type impurity.
Above impurity, major part can be removed by extraction, stripping, ion exchange, evaporation, rectificating method；But the impurity that some of them chemical property is similar to caprolactam, boiling point is close with caprolactam, such as amine, amide-type, carboxylic acid and ester, phenol etc., the polyreaction of nylon-6 monomer can be participated in, amide groups, carboxyl or amido and carbonyl in strand are combined, close end group, terminating chain increases, but is difficult to be removed by said method.
At present, the method removing this type of impurity has two kinds: one is with potassium permanganate oxidation method, a certain amount of potassium permanganate addition crude caprolactam will carry out oxidation processes, caprolactam water solution is dehydrated successively, after removing low-boiling-point substance and high-boiling components, add Caustic soda, be re-fed into finished product treating column, obtain caprolactam final mean annual increment solution, but this method is difficult to control；Another kind is hydrofinishing method, i.e. with hydrogen, oneself the interior phthalein amine aqueous containing trace unsaturation impurity is carried out hydrofinishing, then is isolated by the method for distillation.
Hydrofinishing caprolactam is one of important step producing caprolactam, and the method for industrial hexanolactam hydrofining has following several:
(1) CSTR, catalyst used is that skeleton nickel (has another name called Raney's nickel, English name Raney Ni) catalyst, reacted material separating and filtering together with catalyst, there is complex process and separate difficulty in this method, and catalyst utilization is low, consumption big, cost of equipment is high；
(2) magnetic stablizing bed technique, method disclosed in CN1272491A is that caprolactam water solution contacts with hydrogen in the presence of nickeliferous hydrogenation catalyst and carries out hydrogenation reaction, and reaction is carried out in magnetic stablizing bed with gas-liquid-solid three-phase；Method disclosed in CN1331074A is caprolactam water solution first to be mixed in a mixer with hydrogen, makes the caprolactam water solution containing dissolved hydrogen contact with nickel-containing hydrogenationcatalysts the most again and carries out hydrofinishing, and reaction is biphase to carry out in magnetic stablizing bed with liquid-solid；Method disclosed in CN1552698A is that caprolactam water solution first first carries out gas-liquid-solid phase reaction with catalyst with hydrogen in stirred tank reactor, and make hydrogen be dissolved in caprolactam water solution, then caprolactam water solution enter together with catalyst more magnetic stablizing bed in carry out liquid-solid reaction；The method is the most relatively advanced method.
The type of reactor that above two hydrogenation technique uses is slurry reactor, there is catalyst and is easy to run off, is both needed to recycle and reuse catalyst and the shortcoming of operation complexity.
Disclosed in EP411455A, method is: using gas-liquid-solid three-phase fixed-bed process system, in the presence of a catalyst, caprolactam water solution passes through the fixed bed equipped with catalyst together with hydrogen bottom-up；Disclosed in EP635487A, method is: hydrogen first contacts at stirred tank reactor with caprolactam water solution and dissolves, the caprolactam water solution containing dissolved hydrogen is carried out in fixed bed liquid-solid hydrogenation reaction the most again, this hydrogenation technique flow process is simple, but mass transfer effect is poor, thus hydrogenation reaction carries out the most thorough.
Summary of the invention
The purpose of this utility model is for the deficiencies in the prior art, develops the device of a kind of fixed bed hydrogenation refined caprolactam.
The technical solution of the utility model is: a kind of fixed bed hydrogenation refined caprolactam device, main by feed heater, blender, fixed bed hydrogenation reactor, discharging surge tank, hydrogenation discharging pump composition, it is characterized in that: impure crude caprolactam water solution enters feed heater by pipeline, feed heater is connected with pipe-line mixer import, pipe-line mixer outlet is dissolved stirred tank with hydrogenation and is connected, hydrogenation dissolves stirred tank and is connected with fixed bed hydrogenation reactor, fixed bed hydrogenation reactor is connected with discharging surge tank, discharging surge tank is connected with hydrogenation discharging pump, the described connection between each equipment is to be connected by pipeline.
Described blender is pipe-line mixer, hydrogenation dissolving stirred tank or tower blender.
Described blender is dissolved stirred tank by pipe-line mixer, hydrogenation and forms.
Described pipe-line mixer has crude caprolactam water solution and hydrogen inlet.
Described hydrogenation dissolves stirred tank and also has hydrogen feed tube, blow-down pipe, relief valve and corresponding instrument facility.
Raw hydrogen can respectively enter pipe-line mixer and hydrogenation dissolves stirred tank.
Described fixed bed hydrogenation reactor top arranges liquid distribution trough；Being provided with hydrogen feed tube in reactor head, conversion zone bottom is provided with tail hydrogen delivery pipe, and bottom is material outlet pipe.
Described hydrogenation dissolves agitator material and flows automatically to fixed bed hydrogenation reactor by pressure.
Described fixed bed hydrogenation reactor top arranges liquid distribution trough；Being provided with hydrogen discharge pipe in reactor head, conversion zone bottom is provided with hydrogen feed tube, and bottom is material outlet pipe.
Described fixed bed hydrogenation reactor can be two following currents in parallel or adverse current connection.
Described fixed bed hydrogenation reactor can be that two series connection following currents connect.
The application in caprolactam refining of the fixed bed hydrogenation refined caprolactam device:
Impure crude caprolactam water solution through feed heater heat after with first strand of hydrogen after pipe-line mixer mix, enter hydrogenation stirred tank in mixing, make hydrogen degree of saturation in caprolactam water solution reach 30 ~ 100%；Then in the presence of any one, the crude caprolactam water solution containing dissolved hydrogen and second strand of hydrogen are carried out sufficient gas-liquid-solid hydrogenation reaction in fixed bed reactors at a kind of load-type nickel or palladium fixed bed hydrogenation catalyst；Crude caprolactam water solution mass concentration is 10% ~ 95%；Hydrogenation reaction temperature range is 40 ~ 150 DEG C, and pressure is 0.1 ~ 3.0MPa, and the air speed of caprolactam solution is 1 ~ 50h-1。
Described crude caprolactam water solution mass concentration is 10% ~ 95%, preferably 10% ~ 40%.
First strand of described hydrogen is 0.001 ~ 50 with the mol ratio of caprolactam, preferably 0.1 ~ 10, and second strand of described hydrogen is 0.001 ~ 50 with the mol ratio of caprolactam, preferably 0.1 ~ 10.
Described hydrogenation catalyst is any one in the load-type nickel of current industrial use or palladium fixed bed hydrogenation catalyst, and particle diameter is 0.05 ~ 100mm, preferably 0.5 ~ 10mm.
In described method, reaction temperature is 40 ~ 150 DEG C, preferably 70 ~ 120 DEG C, and reaction pressure is 0.1 ~ 3.0 MPa, preferably 0.5 ~ 1.0 MPa, and air speed is 1 ~ 50h-1, preferably 2 ~ 10h-1。
The shape of fixed bed reactors used is had no particular limits by this utility model in the application, preferably trickle bed reactor；The occupation mode of fixed bed is not particularly limited, and can parallel connection can also connect, and can use with separate unit can also one to open one standby, and gas-liquid flows to have no special requirements, can with gas and liquid flowing downwards, upwards or liquid is downward, on gas-phase reverse flows to, preferably gas and liquid flowing is downward.The method is under the ability ensureing hydrogenation effect, and continuously and easier, more convenient operation, catalyst consumption is lower for flow process.
Accompanying drawing explanation
Fig. 1: two fixed bed parallel connection co-current process devices；
Fig. 2: two fixed bed parallel connection counter-current process devices；
Fig. 3: two fixed bed series connection co-current process devices；
Fig. 4: separate unit fixed bed co-current process device；
Fig. 5: tower blender fixed-bed process device.
In figure: first strand of Hydrogen Line of 1-；2-crude caprolactam water solution pipeline；3-tentatively mixes hydrogen crude caprolactam water solution pipeline；Crude caprolactam water solution pipeline after the molten hydrogen of 4-；Second strand of Hydrogen Line of 5-；6-tail hydrogen pipeline；7-reacted caprolactam water solution pipeline；8-surge tank discharge pipe；9-is hydrogenated with discharging pump discharge pipe；11-feed heater；12-pipe-line mixer；13-hydrogenation dissolves stirred tank；14-fixed bed hydrogenation reactor；14-1-the first fixed bed hydrogenation reactor；14-2 the second fixed bed hydrogenation reactor；15-discharging surge tank；16-is hydrogenated with discharging pump；The tower blender of 17-.
Detailed description of the invention
Below by embodiment, this utility model method during specifically used is further described.
Embodiment 1
(mass concentration is 30% to the impure crude caprolactam water solution of 40 ton hour, PM value is 30s) with first strand of hydrogen stream after pipe-line mixer mixes, enter hydrogenation to dissolve and in parallel with second strand of hydrogen after stirred tank is sufficiently mixed enter reactor, hydrogen and liquid are flowed into reactor by reactor top, such as Fig. 1；Fixed bed reactors top arranges liquid distribution trough；Pressure is 0.9MPa (A), and air speed is 7h-1, per share hydrogen is about 0.9 with the mol ratio of caprolactam；Used catalyst is Ni-based graininess hydrogenation catalyst, and particle diameter is 2.5mm；Dissolved hydrogen and impurity carry out sufficient mass transfer at catalyst surface and react, and the PM value of reacted caprolactam can reach more than 1500s.
Embodiment 2
The impure crude caprolactam water solution (mass concentration is 30%, and PM value is 30s) of 40 ton hour with first strand of hydrogen stream, enters hydrogenation and dissolves and in parallel with second strand of hydrogen after stirred tank is sufficiently mixed enter reactor after pipe-line mixer mixes；Liquid is flowed into reactor by reactor top, and second strand of hydrogen is entered reactor by bottom, such as Fig. 2；Fixed bed reactors top arranges liquid distribution trough；Pressure is 0.8MPa, and air speed is 5h-1, per share hydrogen is about 0.7 with the mol ratio of caprolactam；Used catalyst is Ni-based beaded catalyst；Hydrogen carries out sufficient mass transfer with impurity under catalyst action and reacts, and flows out bottom reacted caprolactam water solution autoreactor, and the PM value of reacted caprolactam solution can reach more than 1500s.
Embodiment 3
The impure crude caprolactam water solution (mass concentration is 30%, and PM value is 30s) of 40 ton hour with first strand of hydrogen stream, enters after hydrogenation dissolving stirred tank is sufficiently mixed and enters the first reactor after pipe-line mixer mixes；Second strand of hydrogen also flows entrance reactor, from the first reactor feed liquid out again with hydrogen and flow entrance the second reactor, such as Fig. 3；Fixed bed reactors top arranges liquid distribution trough；Pressure is 0.8MPa, and air speed is 6h-1, per share hydrogen is about 0.86 with the mol ratio of raw material；Used catalyst is Ni-based beaded catalyst；Hydrogen carries out sufficient mass transfer with impurity under catalyst action and reacts, and flows out bottom reacted caprolactam water solution autoreactor, and the PM value of reacted caprolactam solution can reach more than 1500s.
Embodiment 4
The impure crude caprolactam water solution (mass concentration is 30%, and PM value is 30s) of 40 ton hour with first strand of hydrogen stream, enters hydrogenation dissolving stirred tank and is sufficiently mixed rear and second strand of hydrogen and flows entrance reactor, such as Fig. 4 after pipe-line mixer mixes；Fixed bed reactors top arranges liquid distribution trough；Pressure is 1.0MPa, and air speed is 5h-1, per share hydrogen is about 0.9 with the mol ratio of raw material；Used catalyst is Ni-based beaded catalyst；Hydrogen carries out sufficient mass transfer with impurity under catalyst action and reacts, and flows out bottom reacted caprolactam water solution autoreactor, and the PM value of reacted caprolactam solution can reach more than 1500s.
Embodiment 5
The impure crude caprolactam water solution (mass concentration is 30%, and PM value is 30s) of 40 ton hour enters tower blender top, and the hydrogen entered with bottom at Ta Nei mixes, such as Fig. 5；Mixed liquor enters reactor from the bottom discharge of tower, and the discharge hydrogen of top of tower is also into reactor；Fixed bed reactors top arranges liquid distribution trough；Pressure is 1.0MPa, and air speed is 5h-1, hydrogen is about 0.9 with the mol ratio of raw material；Used catalyst is Ni-based beaded catalyst；Hydrogen carries out sufficient mass transfer with impurity under catalyst action and reacts, and flows out bottom reacted caprolactam water solution autoreactor, and the PM value of reacted caprolactam solution can reach more than 1800s.
Embodiment 6
The impure crude caprolactam water solution (mass concentration is 30%, and PM value is 30s) of 40 ton hour and first strand of hydrogen stream enter hydrogenation dissolving stirred tank and are sufficiently mixed rear and second strand of hydrogen and flow entrance reactor；Fixed bed reactors top arranges liquid distribution trough；Pressure is 1.0MPa, and air speed is 5h-1, per share hydrogen is about 0.9 with the mol ratio of raw material；Used catalyst is Ni-based beaded catalyst；Hydrogen carries out sufficient mass transfer with impurity under catalyst action and reacts, and flows out bottom reacted caprolactam water solution autoreactor, and the PM value of reacted caprolactam solution can reach more than 1480s.
Claims (10)
1. a fixed bed hydrogenation refined caprolactam device, by feed heater (11), blender, fixed bed hydrogenation reactor (14), discharging surge tank (15), hydrogenation discharging pump (16) composition, it is characterized in that: impure crude caprolactam water solution enters feed heater (11) by pipeline, feed heater (11) is connected with pipe-line mixer (12) import, pipe-line mixer (12) export be hydrogenated with dissolving stirred tank (13) be connected, hydrogenation dissolves stirred tank (13) and is connected with fixed bed hydrogenation reactor (14), fixed bed hydrogenation reactor (14) is connected with discharging surge tank (15), discharging surge tank (15) is connected with hydrogenation discharging pump (16), connection between each equipment is to be connected by pipeline.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that described blender is pipe-line mixer (12), hydrogenation dissolving stirred tank (13) or tower blender.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that described blender is dissolved stirred tank (13) by pipe-line mixer (12), hydrogenation and forms.
4. according to the fixed bed hydrogenation refined caprolactam device described in Claims 2 or 3, it is characterised in that described hydrogenation dissolves stirred tank and also has hydrogen feed tube.
Fixed bed hydrogenation refined caprolactam device the most according to claim 3, it is characterised in that described pipe-line mixer has crude caprolactam water solution and hydrogen inlet.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that described fixed bed hydrogenation reactor top arranges liquid distribution trough；Being provided with hydrogen feed tube in reactor head, conversion zone bottom is provided with tail hydrogen delivery pipe, and bottom is material outlet pipe.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that described fixed bed hydrogenation reactor top arranges liquid distribution trough；Being provided with hydrogen discharge pipe in reactor head, conversion zone bottom is provided with hydrogen feed tube, and bottom is material outlet pipe.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that described fixed bed hydrogenation reactor is two following currents in parallel or adverse current connection.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that described fixed bed hydrogenation reactor is that two series connection following currents connect.
Fixed bed hydrogenation refined caprolactam device the most according to claim 1, it is characterised in that hydrogenation dissolves stirred tank material and flows automatically to fixed bed hydrogenation reactor by pressure.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511185A (en) * | 2019-09-17 | 2019-11-29 | 沧州旭阳化工有限公司 | Caprolactam rearrangement device and method |
| CN113896682A (en) * | 2021-09-01 | 2022-01-07 | 湖北三宁化工股份有限公司 | Caprolactam hydrogenation reaction and separation integrated method and system |
| CN115178191A (en) * | 2022-07-28 | 2022-10-14 | 扬州晨化新材料股份有限公司 | Polyether amine continuous production system and method |
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2016
- 2016-05-23 CN CN201620467569.3U patent/CN205761055U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511185A (en) * | 2019-09-17 | 2019-11-29 | 沧州旭阳化工有限公司 | Caprolactam rearrangement device and method |
| CN113896682A (en) * | 2021-09-01 | 2022-01-07 | 湖北三宁化工股份有限公司 | Caprolactam hydrogenation reaction and separation integrated method and system |
| CN115178191A (en) * | 2022-07-28 | 2022-10-14 | 扬州晨化新材料股份有限公司 | Polyether amine continuous production system and method |
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