CN1249031C - Process for refining aqueous hexanolactam solution by hydrogenation - Google Patents
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Abstract
The present invention relates to a process for hydrorefining a caprolactam aqueous solution. In the process, a caprolactam aqueous solution and hydrogen are in contact with ferromagnetic catalysts in a stirred tank reactor to make gas-liquid-solid hydrorefining reaction carried out and make the hydrogen dissolved in 15 to 95 wt% caprolactam aqueous solution first, wherein the caprolactam aqueous solution contains impurities; in addition, the saturation degree of the hydrogen in the caprolactam aqueous solution can be from 50 to 100%; then the caprolactam aqueous solution containing dissolved hydrogen and the catalysts from the stirred tank reactor are fed in a reactor of a magnetic stable bed together to make liquid-solid hydrorefining reaction carried out, and the catalysts are held in the reactor of the magnetic stable bed; one part of the catalysts intermittently or continuously led out from the reactor of the magnetic stable bed are circulated back to the stirred tank reactor. A caprolactam aqueous solution having high concentration can be directly refined by the method, and the method has the advantages of high reaction efficiency and low catalyst consumption.
Description
Technical field
The invention relates to a kind of method of hexanolactam hydrofining.More particularly, the invention relates to a kind of use has ferromagnetic catalyzer the caprolactam water solution of high density is carried out hydrorefined method.
Technical background
Hexanolactam is the raw material that generates nylon-6.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 directly 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, must remove.Therefore one of important step of producing hexanolactam is exactly the back refining of hexanolactam, that is: make unsaturated impurity saturated by hydrogenation process, and its physical properties and hexanolactam are drawn back, so that by extraction and still-process these impurity are removed.
The process for refining flow process is behind the hexanolactam that adopts in the industry at present: (1) benzene collection: reset the crude caprolactam that obtains and extract with benzene, to remove water miscible impurity; (2) water back extraction: water extracts hexanolactam from benzene-caprolactam mixture, removes oil-soluble impurity, obtains concentration and be 30% caprolactam water solution; (3) ion-exchange: the further adsorbing and removing impurity of spent ion exchange resin; (4) hydrofining: make unsaturated impurity become saturated by the shortening process, its physical properties and hexanolactam are drawn back; (5) evaporation: be 30% caprolactam water solution evaporation concentration to 90% with concentration; (6) rectifying: remove light, heavy constituent, obtain caprolactam product.
Catalyst system therefor is that skeleton nickel (has another name called Raney nickel in the existing hexanolactam hydrofining operation, English Raney Ni by name) catalyzer, the reactor that is adopted is a continuous stirred tank reactor (CSTR), and reacted catalyzer leaches the back recycling with feed liquid by flame filter press.Not only complex process, and catalyst utilization is low, consumption is big, and labor strength is also big.
EP 411455A discloses a kind of purifying process of hexanolactam, and the gas-liquid-solid three-phase fixed-bed process of this process using system is a catalyzer with load type palladium or nickel, and wherein the aqueous solution of hexanolactam and gas phase hydrogen make progress by the fixed bed of catalyzer from the bottom.
EP 635487A 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 caprolactam-water to be contacted with gas phase hydrogen hydrogen is dissolved in this mixture, and the mixture that again this is contained dissolved hydrogen contacts with hydrogenation catalyst in fixed bed and carries out the hydrogenation purifying.The hydrogen of 90-100% is to exist with the form that is dissolved in hexanolactam-water mixture in hydrogenation process.The concentration of the caprolactam water solution that this method is suitable for is 10-95%, preferred 10-40%.
The hydrofinishing process of above-mentioned employing fixed bed, though the simple advantage of flow process is arranged, granules of catalyst is big, and mass transfer effect is poor, and catalyzer is changed inconvenience.
CN 1272491A discloses a kind of hydrofinishing process that is used for caprolactam water solution, and this method is impure caprolactam water solution to be contacted with hydrogen carry out hydrofining in the presence of nickeliferous hydrogenation catalyst.Reaction is carried out in magnetic stablizing bed with gas-liquid-solid three-phase.The concentration of the caprolactam water solution that this method is suitable for is 15-50%, preferred 20-40%.
The disclosed hydrofinishing process that is used for caprolactam water solution of CN 1331074A is that impure caprolactam water solution is mixed at mixing tank with hydrogen earlier, hydrogen is dissolved in the caprolactam water solution, and then the caprolactam water solution that contains dissolved hydrogen is contacted with nickeliferous hydrogenation catalyst carry out hydrofining.Reaction is carried out in magnetic stablizing bed with liquid-solid two-phase.The concentration of the caprolactam water solution that this method is suitable for is 15-50%, preferred 20-40%.
The hydrofinishing process that above-mentioned employing is magnetic stablizing bed, though many advantages are arranged than fixed bed, as: catalyst grain size is little, mass transfer effect is good, catalyzer is changed convenient, but it is applicable to the caprolactam water solution of lower concentration, causes that the liquid treatment amount is big, the hydrogenator volume is big, and when the magnetically stabilized bed reactor diameter was big, the magneticfield coil investment was big, magnetic field is difficult for evenly.
Summary of the invention
Purpose of the present invention is exactly that a kind of new caprolactam water solution process for purification is provided on the basis of above-mentioned prior art, overcomes the shortcoming that exists in the prior art.
Hexanolactam hydrofining process provided by the invention is: be earlier the above caprolactam water solution to 95 weight % of 15-95 weight %, preferred 50 weight % with impure, concentration with hydrogen in stirred-tank reactor with have ferromagnetic Hydrobon catalyst and contact and carry out gas-liquid-solid three-phase hydrofining reaction, and hydrogen is dissolved in the caprolactam water solution, and the degree of saturation of hydrogen in caprolactam water solution reaches 50-100%; Make the caprolactam water solution that contains dissolved hydrogen proceed the liquid-solid phase hydrofining reaction in the magnetically stabilized bed reactor then, and catalyzer is trapped in the magnetically stabilized bed reactor with entering from the ferromagnetic Hydrobon catalyst of having of stirred-tank reactor.Return stirred-tank reactor from magnetically stabilized bed reactor intermittence or continuous extension catalyst recirculation.
Reaction conditions in the wherein said stirred-tank reactor is: temperature is a room temperature to 180 ℃, preferred 40-150 ℃; Pressure is the 0.1-3.0 MPa, preferred 0.1-2.0 MPa; Hydrogen liquid input material volume ratio 0.2-10.0, preferred 0.5-6.0; Catalyst concn is 30ppm-2 weight %, preferred 30-5000ppm; Mixing speed is 30-1000 rev/min, preferred 50-500 rev/min; The residence time is 3-60 minute, preferred 5-40 minute.Under this condition, be enough to make the degree of saturation of hydrogen in caprolactam water solution to reach 50-100%.
Reaction conditions in the wherein said magnetically stabilized bed reactor is: temperature is a room temperature to 180 ℃, preferred 40-150 ℃; Pressure is the 0.1-3.0 MPa, preferred 0.1-2.0 MPa; When volume space velocity is 2-100
-1, preferred 4-80 hour
-1Magneticstrength is the 10-1500 oersted, preferred 100-800 oersted.
Wherein said magnetically stabilized bed reactor is to have uniform magnetic field in reactor, have ferromagnetic catalyzer and attract each other and the reactor of stable existence in reactor owing to the magnetization in this magnetic field.It is made of reactor and externally-applied magnetic field.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.Reactor and parts thereof are made by the good material of magnetic permeability.
Wherein said to have ferromagnetic Hydrobon catalyst can be to have a ferromagnetic various Hydrobon catalyst, preferably Raney nickel catalyst or be the amorphous alloy catalyst of main active component with nickel.The granular size of catalyzer is with 1 micron to 5 millimeters, and preferred 10 microns to 2 millimeters, more preferably the 10-800 micron is advisable.
Here said Raney nickel catalyst is at present industrially generally to use, and except that its main component was Ni, this catalyzer can also contain other compositions such as Mn, Cu, Cr, Mo, the W of 0-20 weight %, also can contain the Fe of 0-50 weight %.
Here said is that the amorphous alloy catalyst of main active component has following composition with nickel: the Al of the Ni of 40-95 weight %, 1-30 weight %, the Fe of 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.This catalyzer is preferably formed: Cr, Mo or the W of the Al of the Ni of 50-90 weight %, 5-20 weight %, the Fe of 1-30 weight % and 0-10 weight %.Be 45 ± 1 ° at 2 θ in the X-ray diffractogram of this catalyzer and locate to occur a mild diffuse maximum.
Method provided by the invention can be operated like this: the said catalyzer of at first packing in magnetically stabilized bed reactor feeds certain electric current then so that the uniform steady magnetic field with required value to be provided in the reactor coil.Caprolactam water solution, hydrogen reach and enter stirred-tank reactor from the catalyzer of catalyst preparation still and the mixture of water (or caprolactam water solution), carry out the partial hydrogenation reaction at this, and hydrogen is dissolved in the caprolactam water solution, the caprolactam water solution that contains dissolved hydrogen after the hydrogenation reaction flows out reactor with catalyzer, enters magnetically stabilized bed reactor by the bottom and proceeds hydrogenation reaction.Because the effect in magnetic field, catalyzer is trapped in the magnetically stabilized bed reactor.Caprolactam water solution behind the hydrogenation flows out from the top of magnetically stabilized bed reactor.Take out the part catalyzer continuously or off and on delivers to the catalyzer configuration still and loops back stirred-tank reactor from magnetic stablizing bed bottom.
Method provided by the invention both had been applicable to that concentration was the following rare caprolactam water solutions of 50 weight %, was applicable to that also concentration is the above dense caprolactam water solutions of 50 weight %.In implementation process, in order to reduce investment outlay, rare caprolactam water solution can be carried out evaporation concentration earlier, adopt method provided by the invention to carry out hydrofining again, to reduce treatment capacity, dwindle the volume of magnetically stabilized bed reactor.
Method provided by the invention is compared the low-concentration caprolactam water solution hydrofinishing process with existing, and the hydrogenator volume is little, invests low.
Hydrofining to the high density caprolactam water solution, method provided by the invention is compared with the 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 be able to promote the interaction between catalyzer, hydrogen and the caprolactam water solution effectively, therefore hydrogenation efficiency improves greatly, the foreign matter content of product is far below still formula method behind the hydrogenation, and catalyst consumption is low, and catalyzer need not separate with reaction mass.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.The present invention compares with the processing method that the caprolactam water solution that hydrogen and the first mixing of caprolactam water solution contain dissolved hydrogen then enters magnetically stabilized bed reactor, stirring tank had both played the effect of reactor, the effect of having played molten hydrogen is arranged, it is little to have the magnetically stabilized bed reactor diameter, invests advantages such as low, that processing power is big.
Embodiment
The following examples will be described further method provided by the invention, but not thereby limiting the invention.
The PM value of using in each embodiment and Comparative Examples is the parameter that is used for characterizing product unsaturated materials content, generally is used to contain the more but sign of the product that content is less of unsaturated materials kind.The measuring method of this value can be with reference to " caprolactam production and application " (" caprolactam production and application " writes group, Beijing: hydrocarbon processing press, publication in 1988).Concrete method is: get the 10g caprolactam water solution and inject an exsiccant 100ml colorimetric cylinder, 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 1.00ml potassium permanganate solution (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 3g analytical pure Co (NO
3)
26H
2O and 12mg analytical pure K
2Cr
2O
7Water-soluble, be diluted to 1L, mixing.
Embodiment 1
What present embodiment explanation the present invention was used is the preparation of the amorphous alloy catalyst of main active component with nickel.
48g nickel, 48g aluminium, 1.5g iron, 2.5g 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 is sprayed onto on the copper roller that a rotating speed is 800rpm from the nozzle under the silica tube then, 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 the 70 μ m 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 the 500g20% 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, is kept in the water it standby.Prepared catalyzer is numbered catalyzer-1, and it consists of Ni
75Fe
2.3Cr
3.9Al
18.8
Embodiment 2
What present embodiment explanation the present invention was used is the preparation of the amorphous alloy catalyst of main active component with nickel.
80g nickel is joined in the silica tube with 50g aluminium, 2g iron, it is heated to fusion more than 1450 ℃ in high frequency furnace, make its alloying, indifferent gas with 0.08MPa is sprayed onto this alloy liquid on the copper roller that one rotating speed is 1000rpm from the nozzle under the silica tube then, 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 the 70 μ m through being ground to particle diameter, obtains mother alloy.Get this mother alloy powder of 50g, slowly join in the aqueous solution that 50gNaOH and 250g water is made into, 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-2, and it consists of Ni
87.1Fe
2.2Al
10.7
Embodiment 3
The used Raney nickel catalyst of present embodiment explanation the present invention.The conventional Raney nickel that uses in the prior art that this catalyzer system is sold by the catalyst plant production of Yangzhou, Jiangsu Province is kept at the pH value and is in 13 the buck standby.This catalyzer is designated as catalyzer-3.
Embodiment 4-6
These embodiment illustrate that method provided by the invention is applicable to the hydrofining of different high density caprolactam water solutions.
It is 0.5m that reaction raw materials, hydrogen and catalyzer-1 introduced volume continuously
3Stirred-tank reactor in carry out hydrogenation reaction.Reaction conditions is: 90 ℃ of temperature, pressure 1MPa, reaction raw materials flow 1.5m
3/ h, hydrogen/material volume ratio 1.0, catalyst concn 500ppm, mixing speed 200rpm.
The 90kg granularity of packing in internal diameter is the magnetically stabilized bed reactor of 300mm is the catalyzer-1 of 70-120 μ m; Six internal diameters for 500mm, so that uniform magnetic field to be provided, the distance between the coil is 100mm to height along the reactor axial arranging for 500mm, coil.
After behind above-mentioned hydrogenation, containing the caprolactam water solution of dissolved hydrogen and mixture of catalysts and from stirred-tank reactor, flowing out, enter magnetically stabilized bed reactor from the bottom again, flow out from top, 90 ℃ of temperature, pressure 0.7MPa proceeds hydrofining reaction under the condition of magneticstrength 3200e.Wherein reaction raw materials is the caprolactam water solution of different high densitys: contain the aqueous solution of hexanolactam 70 weight %, the PM value is 25 seconds, and note is made raw material-1; The aqueous solution that contains hexanolactam 80 weight %, PM value are 20 seconds, and note is made raw material-2; The aqueous solution that contains hexanolactam 90 weight %, PM value are 15 seconds, and note is made raw material-3.The gained result is as shown in table 1.
Table 1
| Embodiment | Raw material | PM value behind the hydrogenation, second |
| 4 5 6 | Raw material-1 raw material-2 raw material-3 | 1800 1600 1200 |
Embodiment 7-8
These embodiment illustrate the hydrogenation effect when method provided by the invention adopts different catalysts.
According to the method for describing among the embodiment 4-6 raw material-1 is carried out hydrofining, different is to adopt different catalyzer, the results are shown in table 2.
As can be seen from Table 2, when adopting method provided by the invention to use different catalysts to carry out hexanolactam hydrofining, all has good hydrofining effect.
Table 2
| Embodiment | Catalyzer | PM value behind the hydrogenation, second |
| 7 8 | Catalyzer-2 catalyzer-3 | 1750 1500 |
Embodiment 9-11
These embodiment illustrate the asynchronous hydrogenation effect of catalyst concn in the stirred-tank reactor.
According to the method for describing among the embodiment 4-6 raw material-1 is carried out hydrofining, use catalyzer-1, different is catalyst concn difference in the stirring tank, and the results are shown in Table 3.
Table 3
| Embodiment | Catalyst concn ppm in the still | PM value behind the stirring tank hydrogenation, second | PM value behind the magnetic stablizing bed hydrogenation, second |
| 9 10 11 | 100 800 1200 | 160 300 400 | 1500 2000 2300 |
Embodiment 12-14
These embodiment illustrate that method provided by the invention is equally applicable to the hydrofining of different low-concentration caprolactam water solutions.
According to the method for describing among the embodiment 4-6 caprolactam water solution of different lower concentrations is carried out hydrofining, wherein: contain the aqueous solution of hexanolactam 30 weight %, the PM value is 50 seconds, and note is made raw material-4; The aqueous solution that contains hexanolactam 30 weight %, PM value are 30 seconds, and note is made raw material-5; The aqueous solution that contains hexanolactam 40 weight %, PM value are 25 seconds, and note is made raw material-6.The gained result is as shown in table 4.
Table 4
| Embodiment | Raw material | PM value behind the hydrogenation, second |
| 12 13 14 | Raw material-4 raw material-5 raw material-6 | 3100 2000 1900 |
Comparative Examples
This Comparative Examples has illustrated magnetic stablizing bed technology and the difference of processing method provided by the invention aspect operational condition and reaction effect that adopts continuous stirred tank formula hexanolactam hydrofining technology, adopts dissolved hydrogen.The results are shown in Table 5.
As can be seen from Table 5, compare with the continuously stirring caldron process, technology provided by the invention has good hydrogenation effect; Compare with the magnetic stablizing bed technology that adopts dissolved hydrogen, technology provided by the invention has that processing power is big, the hydrogenation good effectiveness.
Table 5
| Comparative Examples 1 | Comparative Examples 2 | Embodiment | |
| Catalyzer | Catalyzer-1 | Catalyzer-1 | Catalyzer-1 |
| Raw material | Raw material-1 | Raw material-1 | Raw material-1 |
| Type of reactor | Continuous stirred tank reactor (CSTR) | Magnetic stablizing bed | Stirring tank+magnetic stablizing bed |
| Hydrogen enters the mode of reactor | Directly enter with gaseous state | Dissolved hydrogen | - |
| Hydrogen pressure, MPa | 0.7 | 0.7 | 1.0/0.7 |
| Temperature, ℃ | 90 | 90 | 90 |
| Hydrogen/raw material (volume ratio) | 1.5 | 1.0 | 1.0 |
| Catalyst concn, ppm | 50 | - | 500 (stirring tanks) |
| The residence time, min | 20 | - | 10 (stirring tanks) |
| Air speed, the time -1 | - | 30 | 40 (magnetic stablizing bed) |
| PM value behind the hydrogenation, second | 260 | 1200 | 1800 |
Claims (7)
1, a kind of hexanolactam hydrofining process, it is characterized in that this method comprise earlier with impure, concentration be the above caprolactam water solution to 95 weight % of 50 weight % with hydrogen in stirred-tank reactor with have ferromagnetic Hydrobon catalyst and contact and carry out gas-liquid-solid three-phase hydrofining reaction, and hydrogen is dissolved in the caprolactam water solution, and the degree of saturation of hydrogen in caprolactam water solution reaches 50-100%; The caprolactam water solution that contains dissolved hydrogen is entered with the catalyzer from stirred-tank reactor carry out the liquid-solid phase hydrofining reaction in the magnetically stabilized bed reactor, wherein said to have ferromagnetic Hydrobon catalyst be Raney nickel catalyst or have following composition: the Ni of 40-95 weight %, the Al of 1-30 weight %, the Fe of 0-50 weight %, and being selected from of 0-10 weight % by Co, Cr, a kind of metal in the group that Mo and W formed is 45 ± 1 ° of amorphous alloy catalysts of locating to occur a mild diffuse maximum at 2 θ in its X-ray diffractogram.
2, according to the process of claim 1 wherein that the composition of said amorphous alloy catalyst is the Fe of Al, 1-30 weight % of Ni, 5-20 weight % of 50-90 weight % and Cr, Mo or the W of 0-10 weight %.
3, according to the method for claim 1, wherein the reaction conditions in the stirred-tank reactor is: temperature is a room temperature to 180 ℃, pressure is the 0.1-3.0 MPa, hydrogen liquid input material volume ratio 0.2-10.0, catalyst concn is 30ppm-2 weight %, mixing speed is 30-1000 rev/min, and the residence time is 3-60 minute.
4, according to the method for claim 3, the reaction conditions in the wherein said stirred-tank reactor is: temperature is 40-150 ℃, and pressure is the 0.1-2.0 MPa, hydrogen liquid input material volume ratio 0.5-6.0, catalyst concn is 30-5000ppm, and mixing speed 50-500 rev/min, the residence time is 5-40 minute.
5, according to the process of claim 1 wherein that the reaction conditions in the said magnetically stabilized bed reactor is: temperature is a room temperature to 180 ℃, and pressure is the 0.1-3.0 MPa, when volume space velocity is 2-100
-1, magneticstrength is the 10-1500 oersted.
6, according to the method for claim 5, the reaction conditions in the wherein said magnetically stabilized bed reactor is: temperature is 40-150 ℃, and pressure is the 0.1-2.0 MPa, and volume space velocity is 4-80 hour
-1, magneticstrength is the 100-800 oersted.
7, according to the process of claim 1 wherein also comprise enter magnetic stablizing bed, be trapped in the magnetically stabilized bed reactor from the ferromagnetic Hydrobon catalyst of having of stirred-tank reactor; Return stirred-tank reactor from magnetically stabilized bed reactor intermittence or continuous extension catalyst recirculation.
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| CN 03137925 CN1249031C (en) | 2003-05-30 | 2003-05-30 | Process for refining aqueous hexanolactam solution by hydrogenation |
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103086968A (en) * | 2013-02-22 | 2013-05-08 | 湖南百利工程科技股份有限公司 | Method for refining caprolactam through fixed-bed hydrogenation |
| 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 |
| CN104072419B (en) * | 2013-10-28 | 2016-11-02 | 中国石油化工股份有限公司 | The purification process of a kind of caprolactam and purification devices |
| CN104557707B (en) * | 2013-10-28 | 2017-02-08 | 中国石油化工股份有限公司 | Caprolactam hydrofining method |
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