CN1119333C - Process for hydrorefining caprolactam - Google Patents
Process for hydrorefining caprolactam Download PDFInfo
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- CN1119333C CN1119333C CN 00109588 CN00109588A CN1119333C CN 1119333 C CN1119333 C CN 1119333C CN 00109588 CN00109588 CN 00109588 CN 00109588 A CN00109588 A CN 00109588A CN 1119333 C CN1119333 C CN 1119333C
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Abstract
The present invention provides a method for hydrorefining caprolactam, which is characterized in that the method comprises the steps that a caprolactam aqueous solution containing impurities comes into contact with hydrogen gas in a mixer to be thoroughly mixed to make the hydrogen gas dissolved in the caprolactam aqueous solution; then, in a reactor of a magnetic stable bed, the caprolactam aqueous solution containing dissolved oxygen comes into contact with a ferromagnetic hydrorefining catalyst to carry out hydrorefining reaction under the conditions that the room temperature is 180 DEG C below zero, normal pressure is 3.0 MPas below zero, weight space velocity is 2 to 100 hrs <-1>, magnetic field strength is from 10 to 1500 Ost and the saturation level of hydrogen in the caprolactam aqueous solution is from 50 to 100%. Compared with a process method of the existing continuous stirred tank reactor, the method of the present invention has the advantages of high efficiency, low catalyst consumption, no separation of catalysts from reaction materials, continuous and simple process and convenient operation.
Description
Technical field
The present invention relates to a kind of hexanolactam hydrofining process.
Background technology
Hexanolactam is the raw material that generates nylon-6.Refining behind the hexanolactam is the important step of producing hexanolactam.The production of hexanolactam comprises that prepared from benzene and hydrogen hexanaphthene, cyclohexane oxidation preparing cyclohexanone, pimelinketone oximate preparing cyclohexanone oxime, cyclohexanone-oxime transposition generate processes such as hexanolactam, in these production processes, except that hexanolactam, also can generate some undersaturated by products.The physico-chemical property of these unsaturated by products and hexanolactam are very approaching, are difficult to remove by extraction and still-process.And the existence of these impurity will influence the caprolactam polymerization process, be directly connected to the quality of nylon-6 product, therefore must remove.Refiningly behind the hexanolactam make unsaturated impurity saturated by hydrogenation process with exactlying, its physical properties and hexanolactam are drawn back, so that by extracting and still-process is removed these impurity.Catalyst system therefor is a skeleton nickel (Raney nickel in the existing hexanolactam hydrofining technology, English Raney Ni by name) catalyzer, the reactor that is adopted is a continuous stirred tank reactor (CSTR), post catalyst reaction leaches the back recycling with feed liquid by flame filter press, complex process, catalyst utilization is low, consumes greatly, and labor strength is big.
EP-A-411455 discloses a kind of purifying process of hexanolactam, the gas-liquid-solid three-phase fixed-bed process of this process using system, with load type palladium or nickel is catalyzer, and wherein the aqueous solution of hexanolactam and gas phase hydrogen make progress by the fixed bed of catalyzer from the bottom.
EP-A-635487 discloses a kind of hydrogenation technique of purifying of the mixture that is used for hexanolactam and water, this technology is earlier the mixture of hexanolactam-water to be contacted with gas phase hydrogen hydrogen is dissolved in this mixture, the mixture that then this is contained dissolved hydrogen contacts with hydrogenation catalyst in fixed bed and carries out the hydrogenation purifying, and the hydrogen of 90-100% is to exist with the form that is dissolved in hexanolactam-water mixture in hydrogenation process.Adopt this method can improve hydrogenation efficiency, improved security simultaneously.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of hydrogenation efficiency higher, the novel hexanolactam hydrofining process that removal of impurity ability is stronger.
Hexanolactam hydrofining process provided by the present invention comprises that elder generation contacts impure caprolactam water solution and hydrogen in mixing tank and thorough mixing is dissolved in the caprolactam water solution hydrogen, the caprolactam water solution that then this is contained dissolved hydrogen is a room temperature-180 ℃ in temperature in magnetically stabilized bed reactor, pressure is normal pressure-3.0 MPa, and weight space velocity is 2-100 hour
-1, magneticstrength is 10-1500 oersted (Oe), the degree of saturation of hydrogen in caprolactam water solution is to have ferromagnetic Hydrobon catalyst and contact and carry out hydrofining reaction with a kind of under the condition of 50-100%; Wherein said magnetically stabilized bed reactor is to have uniform magnetic field in reactor, has ferromagnetic catalyzer and attracts each other and the reactor of stable existence in reactor owing to the magnetization in this magnetic field.
The mixing tank of said caprolactam water solution and hydrogen has no particular limits in the hexanolactam hydrofining process provided by the invention, can be stirring tank formula mixing tank, tube mixer or the like; Said blended condition is that temperature is room temperature-180C, pressure is the 0.1-3.0 MPa, the volume ratio of hydrogen and caprolactam water solution is 0.2-20, and the blended result makes hydrogen have the degree of saturation of 50-100% under this mixing condition in caprolactam water solution.
Said magnetically stabilized bed reactor is made of reactor and externally-applied magnetic field in the hexanolactam hydrofining process provided by the invention, externally-applied magnetic field is along the axial uniform steady magnetic field of reactor, uniform magnetic field is by direct supply and a series of and co-axial helmholtz coil of reaction tubes or evenly closely provide around solenoid coil, and other parts of reactor and reactor are made by the good material of magnetic permeability.
The concentration of said caprolactam water solution is 15-50 weight % in the hexanolactam hydrofining process provided by the present invention, is preferably 20-40 weight %.
Said catalyzer can be to be used for hydrorefined various catalyzer in the hexanolactam hydrofining process provided by the invention, but must be to have ferromagnetic catalyzer, wherein preferably use Raney nickel catalyst or with the amorphous alloy catalyst of nickel as main active component.In order to strengthen the magnetic of catalyzer, this catalyzer can contain iron.Granules of catalyst can place magnetically stabilized bed reactor separately, and perhaps the iron powder that also can mix the 10-200% catalyst weight for the magnetic that increases catalyzer mixes and to place magnetically stabilized bed reactor.The granular size of catalyzer is with 1 micron to 5 millimeters, and preferred 10 microns to 2 millimeters, more preferably the scope of 10-800 micron is advisable.Said catalyzer can be present in the reactor with the fixed bed form, also can pass in and out reactor with continuous or intermittent mode according to the needs of operation.
Said Raney nickel catalyst is the at present industrial Raney nickel catalyst that generally uses in the hexanolactam hydrofining process provided by the invention, this catalyzer can contain other active ingredients such as Mn, Cu, Cr, Mo or W of 0-20 weight %, also can contain the iron of 0-50 weight %.
Said amorphous alloy catalyst is the amorphous alloy catalyst that contains Ni in the hexanolactam hydrofining process provided by the invention, be 45 ± 1 ° at 2 θ in the X-ray diffractogram of this catalyzer and locate to occur a diffuse maximum (steamed bun shape diffuse scattering peak) that the Fe of the Al of the Ni that consists of 40-95 weight % of this catalyzer, 1-30 weight %, the P of 0-25 weight %, 0-50 weight % and 0-10 weight % are selected from a kind of metal in the group of being made up of Co, Cr, Mo and W.
Preferably to form be the Fe of P, 1-30 weight % of Al, 0-20 weight % of Ni, 5-20 weight % of 50-90 weight % and Cr, Mo or the W of 0-10 weight % to said amorphous alloy catalyst in the method provided by the invention.
Said blended condition optimization is that temperature is 40-150 ℃ in the method provided by the invention, pressure is 0.1-2.0 MPa (MPa), the volume ratio of hydrogen and caprolactam water solution is 0.5-10, and the degree of saturation of hydrogen in caprolactam water solution is 80-100%.
The condition optimization of said hydrofining reaction is that temperature is 40-150 ℃ in the method provided by the invention, and pressure is 0.1-2.0 MPa (MPa), and weight space velocity is 4-80 hour
-1, magneticstrength is the 100-800 oersted.
The operating process of method provided by the invention can be that the composite grain of at first pack in magnetically stabilized bed reactor said catalyzer or said catalyzer and iron powder feeds certain electric current then so that uniform steady magnetic field to be provided in the reactor coil.Caprolactam water solution and hydrogen thorough mixing in mixing tank enters magnetically stabilized bed reactor by reactor lower part then and carries out gas-liquid-solid three-phase (or liquid-solid two-phase) selective hydrogenation.
Method provided by the invention is compared with existing continuous stirred tank reactor (CSTR) processing method, because catalyzer can disperse in liquid phase under the action of a magnetic field well, and the existence in magnetic field may can promote catalyzer effectively, interaction between hydrogen and the caprolactam water solution, so hydrogenation efficiency improves greatly, the foreign matter content of product is far below existing method behind the hydrogenation, and catalyst consumption is low, catalyzer need not separate with reaction mass, and flow process continuously and simply, and is easy to operate.The present invention compares without mixing the processing method that enters magnetically stabilized bed reactor respectively with caprolactam water solution with hydrogen, and the hydrogen recycle amount is few, the air speed height, and required magneticstrength is low, and energy consumption is low.
Embodiment
The following examples will be described further processing method provided by the invention.
The PM value is usually used in characterizing the content of unsaturated materials in the product, generally is used to contain the more but sign of the product that content is less of unsaturated materials kind.The method of measuring the PM value of caprolactam water solution in each embodiment and Comparative Examples is: get 10 these solution of gram and inject 100 milliliters of colorimetric cylinders of an exsiccant, add deionized water to scale; This colorimetric cylinder and standard colorimetric tube are put on the colorimetric shelf in the water bath with thermostatic control, close the lid, when treating that solution temperature reaches 20 ℃, in solution to be measured, add 1.00 milliliters of potassium permanganate solutions (concentration is 0.002M), start stopwatch immediately, note the time of being experienced when solution colour is identical with reference colour in the colorimetric cylinder (second), this value is exactly the PM value.
The compound method of standard color solution is: with 3000 milligrams of pure Co (NO of top grade
3)
26H
2O and 12 milligrams of pure K of top grade
2Cr
2O
7Water-soluble, be diluted to 1 liter, mixing.
The measuring method of PM value can be with reference to " caprolactam production and application " (" caprolactam production and application " writes group, Beijing: hydrocarbon processing press, publication in 1988).
Embodiment 1
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
48 gram nickel, 48 gram aluminium, 1.5 gram iron, 2.5 gram chromium are joined in the silica tube, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas this alloy liquid being sprayed onto a rotating speed from the nozzle under the silica tube then is on 800 rev/mins the copper roller, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, the flakey band is below 70 microns through being ground to particle diameter, obtains mother alloy.Mother alloy is heat-treated in hydrogen environment, and heat treated temperature is 600 ℃, and constant temperature time is 3 hours.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 500 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 100 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid is 7 with 80 ℃ distilled water washs to pH value.Prepared catalyzer is numbered catalyzer-1, is kept in the water it standby.This catalyzer consist of Ni
75Fe
2.3Cr
3.9Al
8.8
Embodiment 2
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
44 gram nickel, 52 gram aluminium, 2.5 gram iron, 1.5 gram chromium are joined in the silica tube, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas this alloy liquid being sprayed onto a rotating speed from the nozzle under the silica tube then is on 800 rev/mins the copper roller, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, the flakey band is below 70 microns through being ground to particle diameter, obtains mother alloy.Mother alloy is heat-treated in hydrogen environment, and heat treated temperature is 700 ℃, and constant temperature time is 2 hours.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 100 ℃ and constant temperature and stirred 1.5 hours.After stopping heating and stirring, decantation liquid is 7 with 100 ℃ distilled water washs to pH value.Prepared catalyzer is numbered catalyzer-2, is kept in the water it standby.This catalyzer consist of Ni
76Fe
4.3Cr
2.6Al
17.1
Embodiment 3
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
48 gram nickel, 48 gram aluminium, 2.5 gram iron, 1.5 gram molybdenums are joined in the silica tube, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas this alloy liquid being sprayed onto a rotating speed from the nozzle under the silica tube then is on 800 rev/mins the copper roller, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, the flakey band is below 70 microns through being ground to particle diameter, obtains mother alloy.Mother alloy is heat-treated in hydrogen environment, and heat treated temperature is 700 ℃, and constant temperature time is 2 hours.Mother alloy after heat treatment slowly joins in the there-necked flask that fills 1000 grams, 20% aqueous sodium hydroxide solution, controls its temperature and is 100 ℃ and constant temperature and stirred 1.5 hours.After stopping heating and stirring, decantation liquid is 7 with 100 ℃ distilled water washs to pH value.Prepared catalyzer is numbered catalyzer-3, is kept in the water it standby.This catalyzer consist of Ni
79.5Fe
4.1Mo
2.5Al
13.9
Embodiment 4
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
80 gram nickel and 20 gram phosphorus are placed crucible, the heating make its voluntarily alloying make the Ni-P alloy, get this alloy 48 grams, join in the silica tube with 50 gram aluminium, 2 gram iron, it is heated to fusion more than 1300 ℃ in high frequency furnace, make its alloying, with indifferent gas this alloy liquid being sprayed onto a rotating speed from the nozzle under the silica tube then is on 800 rev/mins the copper roller, logical water coolant in the copper roller, alloy liquid is through throwing away along copper roller tangent line after the cooling fast, form the flakey band, the flakey band is placed ventilated environment, below the efflorescence to 50 micron.Get 50 these mother alloy powder of gram, slowly join in the 110 gram NaOH and 450 aqueous solution that are made into of gram water, 0 ℃ was stirred 10 minutes down, stirred 60 minutes down at 40 ℃ then.After stopping heating and stirring, decantation liquid, being washed with distilled water to the pH value is 7, is kept in the water it standby.
Prepared catalyzer is numbered catalyzer-4, and it consists of Ni
60.9Fe
3.2P
13.7Al
22.2
Embodiment 5
The used a kind of Preparation of catalysts of present embodiment explanation the present invention.
80 gram nickel are joined in the silica tube with 50 gram aluminium, 2 gram iron, it is heated to fusion more than 1450 ℃ in high frequency furnace, make its alloying, with the indifferent gas of 0.08MPa this alloy liquid being sprayed onto a rotating speed from the nozzle under the silica tube then is on 1000 rev/mins the copper roller, logical water coolant in the copper roller, alloy liquid forms the flakey band through throwing away along copper roller tangent line after the cooling fast, the flakey band is below 70 microns through being ground to particle diameter, obtains mother alloy.Get 50 these mother alloy powder of gram, slowly join in the 50 gram NaOH and 250 aqueous solution that are made into of gram water, placed 1 hour under the room temperature, be warming up to 80 ℃ of constant temperature then and stirred 2 hours.After stopping heating and stirring, decantation liquid, being washed with distilled water to the pH value is 7, is kept in the water it standby.Prepared catalyzer is numbered catalyzer-5, and it consists of Ni
87.1Fe
2.2Al
10.7
Embodiment 6
The used a kind of catalyzer of present embodiment explanation the present invention, this catalyzer are the conventional Raney nickel catalyst that uses in the prior art, are designated as catalyzer-6, and this catalyzer is sold by the catalyst plant production of Yangzhou, Jiangsu Province, are kept at the pH value and are in 13 the buck standby.
Embodiment 7-13
These embodiment illustrate the influence of magneticstrength to reaction result.
The catalyzer-1 that the 10 milliliters of granularities of packing in internal diameter is 14 millimeters reactor are the 50-70 micron; Seven internal diameters for 55 millimeters, external diameter for 165 millimeters, height for 35 millimeters, the number of turn for 370 coil along the reactor axial arranging so that uniform magnetic field to be provided, the distance between the coil is 27.5 millimeters; Reaction raw materials and hydrogen mixed in stirring tank formula mixing tank after 15 minutes (mixing condition is 90 ℃ of temperature, pressure 1MPa, hydrogen material volume ratio 1.5,500 rev/mins of mixing speed), entered by the magnetically stabilized bed reactor bottom, flow out on top, is 90 ℃ in temperature, pressure is 0.8MPa, and air speed is 30 hours
-1Condition under carry out hydrofining reaction, wherein reaction raw materials is impure caprolactam water solution (contain hexanolactam 30 weight %, the PM value is 110 seconds, down with), the results are shown in Table 1 for gained.The result of table 1 shows that under different magneticstrengties, hexanolactam hydrofining process provided by the invention all has good hydrofining effect.
Table 1
PM value (second) behind embodiment magneticstrength (Oe) hydrogenation
7 101 4800
8 133 5080
9 200 5700
10 230 6200
11 268 6030
12 401 5600
13 535 5500
Embodiment 14-18
Hydrogenation effect when these embodiment explanations are adopted different catalysts in magnetically stabilized bed reactor.
Carry out hydrofining according to the method for describing among the embodiment 7-13, different is to adopt different catalyzer, and the results are shown in Table 2.
As can be seen from Table 2, when adopting method provided by the invention to carry out hexanolactam hydrofining, has good hydrofining effect.
Table 2
PM value (second) behind embodiment catalyzer magneticstrength (0e) hydrogenation
14 catalyzer-2 268 5750
15 catalyzer-3 268 4860
16 catalyzer-4 360 4600
17 catalyzer-5 360 4200
18 catalyzer-6* 150 2600
* in order to improve the magneticstrength of beds, the iron powder of half Raney nickel weight is housed in the reactor.
Embodiment 19-22
These embodiment illustrate the influence of temperature to reaction result.
Carry out the hydrofining of caprolactam water solution according to the method for embodiment 7-13, just change temperature (mixing temperature is identical with temperature of reaction), magneticstrength is 268 Oe, and the results are shown in Table 3 for gained.As can be seen from Table 3, under given raw material and operational condition, with the raising of temperature of reaction, material PM value improves thereupon behind the hydrogenation.
Table 3
The embodiment temperature (℃) PM value (second) behind the hydrogenation
19 40 3200
20 70 5160
21 100 6380
22 120 7200
Embodiment 23-24
These embodiment illustrate the influence of pressure to reaction result.
Carry out the hydrofining of caprolactam water solution according to the method for embodiment 7-13, just change pressure, magneticstrength is 268 0e, and the results are shown in Table 4 for gained.
Table 4
PM value (second) behind embodiment blend pressure (MPa) reaction pressure (MPa) hydrogenation
23 0.5 0.3 3600
24 1.7 1.5 8560
Embodiment 24-27
These embodiment illustrate the influence of air speed to the hydrogenation effect.
Carry out the hydrofining of caprolactam water solution according to the method for embodiment 7-13, just change reaction velocity, magneticstrength is 268 Oe, and the results are shown in Table 5 for gained.
Table 5
The embodiment air speed (hour
-1) PM value (second) behind the hydrogenation
25 10 7200
26 30 6030
27 60 5300
Embodiment 28-30
These embodiment illustrate hydrogen/material comparison hydrogenation reaction result's influence.
Carry out the hydrofining of caprolactam water solution according to the method for embodiment 7-13, just change the hydrogen/material volume ratio when mixing, magneticstrength is 268 Oe, and the results are shown in Table 6 for gained.
Table 6
Embodiment hydrogen/material than (volume ratio) hydrogenation after PM value (second)
28 5.0 6880
29 3.5 6390
30 1.5 6030
Comparative Examples 1-2
This Comparative Examples has contrasted continuously stirring caldron process and the difference of processing method provided by the invention aspect operational condition and reaction effect that adopts gas-liquid-solid three-phase continuous stirred tank formula hexanolactam hydrofining technology, adopts dissolved hydrogen.
As can be seen from Table 7, compare with the continuously stirring caldron process that adopts dissolved hydrogen with gas-liquid-solid three-phase continuously stirring caldron process, technology provided by the invention has good hydrogenation effect, catalyzer flows out with feed liquid in preceding two kinds of technologies simultaneously, the later separation step must be arranged, so flow process is complicated.Adopt technology provided by the invention, catalyzer is controlled in the bed, simplified flow process, also can reduce catalyst consumption simultaneously.
Table 7. hydrogenation technique provided by the invention
With the gas-liquid-solid three-phase caldron process with the comparison of the caldron process of dissolved hydrogen
The mode that Comparative Examples 1 Comparative Examples 2 embodiment 11 catalyst agent-1 catalyzer-1 catalyzer-1 type of reactor continuous stirred tank reactor (CSTR) continuous stirred tank reactor (CSTR) magnetically stabilized bed reactor hydrogen enter reactor directly enters dissolved hydrogen dissolved hydrogen hydrogen pressure with gaseous state, MPa 0.7 0.8 0.8 temperature, ℃ 90 90 90 hydrogen/raw material (volume ratio), 1.5 1.5 1.5 catalyst/feed (weight ratio) 1: 20,000 1: 20000--the residence time, minutes 11 11--air speed, hour
-1One--PM value behind 30 hydrogenation, second 1,800 2,100 6030
Claims (5)
1, a kind of hexanolactam hydrofining process, it is characterized in that this method comprises that elder generation contacts impure caprolactam water solution and hydrogen in mixing tank and thorough mixing is dissolved in the caprolactam water solution hydrogen, the caprolactam water solution that then this is contained dissolved hydrogen is a room temperature-180 ℃ in temperature in magnetically stabilized bed reactor, pressure is normal pressure-3.0 MPa, and weight space velocity is 2-100 hour
-1, magneticstrength is the 10-1500 oersted, the degree of saturation of hydrogen in caprolactam water solution is under the condition of 50-100% to be that the amorphous alloy catalyst of main active component contacts and carries out hydrofining reaction with Raney nickel catalyst or with nickel; Wherein the concentration of said caprolactam water solution is 15-50 weight %; Said caprolactam water solution and hydrogen blended condition are that temperature is a room temperature-180 ℃, pressure is the 0.1-3.0 MPa, the volume ratio of hydrogen and caprolactam water solution is 0.2-20, and the blended result makes hydrogen have the degree of saturation of 50-100% under this mixing condition in caprolactam water solution; Said magnetically stabilized bed reactor is to have uniform magnetic field in reactor, has ferromagnetic catalyzer and attracts each other and the reactor of stable existence in reactor owing to the magnetization in this magnetic field.
2, place magnetically stabilized bed reactor to strengthen the magnetic of catalyzer according to the process of claim 1 wherein the iron powder with respect to the 10-200 weight % of catalyst weight mixed.
3, according to the method for claim 1, wherein said amorphous alloy catalyst is the amorphous alloy catalyst that contains Ni, be 45 ± 1 ° at 2 θ in the X-ray diffractogram of this catalyzer and locate to occur a mild diffuse maximum that the Fe of the Al of the Ni that consists of 40-95 weight % of this catalyzer, 1-30 weight %, the P of 0-25 weight %, 0-50 weight % and 0-10 weight % are selected from a kind of metal in the group of being made up of Co, Cr, Mo and W.
4, according to the method for claim 3, wherein the composition of said amorphous alloy catalyst is the Fe of P, 1-30 weight % of Al, 0-20 weight % of Ni, 5-20 weight % of 50-90 weight % and Cr, Mo or the W of 0-10 weight %.
5, according to the process of claim 1 wherein that the condition of said hydrofining reaction is that temperature is 40-150 ℃, pressure is the 0.1-2.0 MPa, and weight space velocity is 4-80 hour
-1, magneticstrength is the 100-800 oersted.
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CN101070298B (en) * | 2006-05-12 | 2012-01-25 | 中国石油化工股份有限公司 | Method for purifying and refining epsi-caprolactam |
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CN100372610C (en) * | 2004-06-14 | 2008-03-05 | 北京化工大学 | Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use |
CN100345758C (en) * | 2005-09-19 | 2007-10-31 | 北京化工大学 | One-step baking method for preparing magnetic microspheric alumina |
CN101070299B (en) * | 2006-05-12 | 2011-04-20 | 中国石油化工股份有限公司 | Method for purifying and refining Epsilon-caprolactam |
CN102050783B (en) * | 2009-10-30 | 2012-07-25 | 中国石油化工股份有限公司 | Method for hydrofining caprolactam in magnetically stabilized bed |
CN104557707B (en) * | 2013-10-28 | 2017-02-08 | 中国石油化工股份有限公司 | Caprolactam hydrofining method |
CN104557706B (en) * | 2013-10-28 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of hexanolactam hydrofining process |
CN110575799A (en) * | 2019-10-24 | 2019-12-17 | 西南大学 | Tank for researching electromagnetic field chemical effect |
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