CN103145618A - Method for cogeneration of caprolactam and ammonium sulfate - Google Patents
Method for cogeneration of caprolactam and ammonium sulfate Download PDFInfo
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- CN103145618A CN103145618A CN2013100840781A CN201310084078A CN103145618A CN 103145618 A CN103145618 A CN 103145618A CN 2013100840781 A CN2013100840781 A CN 2013100840781A CN 201310084078 A CN201310084078 A CN 201310084078A CN 103145618 A CN103145618 A CN 103145618A
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- Prior art keywords
- ammonium sulfate
- caprolactam
- ammonia
- sulfonate
- hexanolactam
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 91
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 50
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 19
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 239000012452 mother liquor Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 32
- 239000013078 crystal Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000010871 livestock manure Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- RSPWPAYFBOWLKA-UHFFFAOYSA-N cyclohexane;formic acid Chemical compound OC=O.C1CCCCC1 RSPWPAYFBOWLKA-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006146 oximation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for cogeneration of caprolactam and ammonium sulfate. The method comprises a step of injecting caprolactam sulfonate and ammonia into a reactor containing ammonium sulfate mother liquor to carry out neutral reaction. By adopting the method, caprolactam and ammonium sulfate with high yield and purity can be obtained at the same time; and the method has industrial application prospect.
Description
Technical field
The present invention relates to a kind of method of hexanolactam and ammonium sulfate coproduction.
Background technology
Ammonium sulfate is the nitrogen fertilizer that occurs the earliest, and fertilizer efficiency is fast, stable advantages of higher because it has, and is mainly used in being made into multifunctional agricultural fertilizer, compound manure and mixed fertilizer, can be used for also that crop is topdressed, seed manure, base manure etc.In addition, industrial, ammonium sulfate can be used for the aspects such as weaving, leather deliming, pharmacy.
Hexanolactam is the lactan that shrinks and form in the epsilon-amino caproic acid molecule, is a kind of important Organic Chemicals.The main application of hexanolactam is to generate polymeric amide section (being commonly referred to nylon-6 section or nylon-6 section) by polymerization, then further is processed into nylon fibre, engineering plastics, plastics film etc.At present, the preparation method of hexanolactam mainly contains following several: (1) phynol method: phenol hydrocracking under nickel lead alloy catalyzer exists is hexalin; Rectifying separation goes out hexalin, is converted into pimelinketone take zinc, iron or copper as the catalyzer dehydrogenation; Rectifying obtains pimelinketone, generates cyclohexanone-oxime with oxammonium sulfate and ammonia generation oximation reaction, also generates simultaneously by product ammonium sulfate; Isolated cyclohexanone-oxime generates hexanolactam through Beckmann rearrangement under the existence of excessive oleum.(2) cyclohexane oxidation process: benzene is under the existence of nickel catalyzator of carrier at aluminium sesquioxide, obtains hexanaphthene through gas phase hydrogenation reaction; Hexanaphthene generates hexalin and pimelinketone take cobalt as catalyzer through liquid-phase oxidation; Cyclohexanol dehydrogenation is converted into pimelinketone, generates cyclohexanone-oxime with oxammonium sulfate and ammonia generation oximation reaction, also generates simultaneously byproduct of ammonium sulfate; Isolated cyclohexanone-oxime generates hexanolactam through Beckmann rearrangement under excessive oleum exists.(3) toluene method: toluene oxidation under the effect of cobalt salt catalyst generates phenylformic acid, and phenylformic acid carries out liquid-phase hydrogenatin with the palladium catalyst on absorbent charcoal carrier and generates hexahydrobenzene formic acid; In oleum, hexahydrobenzene formic acid and nitrosyl sulfuric acid reaction generate hexanolactam, and use the ammonia neutralization oleum, obtain byproduct of ammonium sulfate.Nearly all can produce byproduct of ammonium sulfate in the production method of hexanolactam at present, but because ammonium sulfate content is lower, be not easy to separate from reaction system.
Summary of the invention
The objective of the invention is for a kind of new hexanolactam and the method for ammonium sulfate coproduction are provided.
The invention provides a kind of method of hexanolactam and ammonium sulfate coproduction, the method comprises: caprolactam sulfonate and ammonia are injected the reactor that is loaded with ammonium sulfate liquor carry out neutralization reaction.
The method of existing hexanolactam and ammonium sulfate coproduction can be for carrying out neutralization reaction with caprolactam sulfonate and ammoniacal liquor.Yet, adopt the reaction process of the method comparatively violent, side reaction is more, and the ammonium sulfate that obtains is difficult to crystallization from reaction system, thereby has reduced the yield of ammonium sulfate.and the present inventor is through finding, caprolactam sulfonate and ammonia are injected the reactor that is loaded with ammonium sulfate liquor carry out neutralization reaction, not only can make reaction become comparatively mild, reduce the generation of side reaction, and the existence of ammonium sulfate liquor also provides nucleus for the crystallization of reacting the ammonium sulfate that generates, thereby make ammonium sulfate crystallization from reaction system at an easy rate, the hexanolactam that generates simultaneously is positioned at the upper strata of system because density is less, can separate with ammonium sulfate at an easy rate, obtain all higher hexanolactam and ammonium sulfate of yield and purity, has prospects for commercial application.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Description of drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and consists of the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the schematic diagram according to the hexanolactam of a kind of embodiment of the present invention and ammonium sulfate co-production.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The method of hexanolactam provided by the invention and ammonium sulfate coproduction comprises: caprolactam sulfonate and ammonia are injected the reactor that is loaded with ammonium sulfate liquor carry out neutralization reaction.
According to the present invention, described ammonia can inject with the form of ammonia, also can inject with the form of ammoniacal liquor.When injecting with the ammoniacal liquor form, the concentration of described ammoniacal liquor is preferably the 10-30 % by weight.Under preferable case, described ammonia injects with the form of ammonia, can avoid so constantly introducing water in reaction system, more is conducive to the crystallization of ammonium sulfate.
The present invention is not particularly limited the consumption of described caprolactam sulfonate and ammonia, as long as can generate simultaneously hexanolactam and ammonium sulfate, but in order to improve the utilization ratio of raw material, take the caprolactam sulfonate of 1mol as benchmark, the consumption of described ammonia is preferably 1-3mol.Need to prove, when ammonia used with the form of ammoniacal liquor, the consumption of ammonia described herein did not comprise the content of water.
The present invention is not particularly limited the condition of described neutralization reaction, and as a rule, described neutralization reaction comprises the temperature of reaction, the pressure of reaction, the pH value of reaction and the time of reaction.Wherein, in order more to be conducive to the carrying out of neutralization reaction, the temperature of described reaction is preferably 45-65 ℃, and the absolute pressure of described reaction is preferably 16-20kPa, and the pH value of reaction is preferably 4.5-6.5.In addition, the prolongation in reaction times is conducive to the raising of reaction-ure conversion-age and reaction product yield, but long amplitude to reaction-ure conversion-age and the raising of reaction product yield of reaction times is also not obvious, therefore, consider effect and efficient, the time of described reaction is preferably 2-10 hour.After reaction finished, hexanolactam separated as light easy and ammonium sulfate liquor as heavy phase mutually, and sends into and make the finished product hexanolactam in follow-up refining step; Continuous evaporation and concentrating under the effect of the neutralization reaction heat that ammonium sulfate liquor produces under by above-mentioned neutralization reaction condition, the state that reaches capacity is separated out with the form of ammonia sulfate crystal, and obtains the export trade of finished product sulfuric acid ammonium packing by subsequent disposal such as centrifugal, dehydrations.
According to the present invention, described ammonium sulfate liquor is the aqueous solution of ammonium sulfate.The present invention is not particularly limited the concentration of described ammonium sulfate liquor, as long as can slow down the severe degree of neutralization reaction and provide nucleus for the crystallization of product ammonium sulfate, for example, the concentration of described ammonium sulfate liquor can be the 10-40 % by weight, is preferably the 20-30 % by weight.
According to the present invention, the consumption of described ammonium sulfate liquor can reasonably be selected according to the size of reactor usually.Under preferable case, the splendid attire liquid level of described ammonium sulfate liquor accounts for the 20-50% that described reactor is deposited liquid level, can guarantee that so on the one hand the ammonium sulfate that generates can fully separate out, can guarantee that on the other hand the hexanolactam that generates can separate by overflow with the ammonium sulfate heavy phase that generates at an easy rate as light phase.
The method of hexanolactam provided by the invention and ammonium sulfate coproduction also preferably includes the step for preparing in accordance with the following methods caprolactam sulfonate: under the existence of oleum, cyclohexanone-oxime is carried out Beckmann rearrangement.
Wherein, under the existence of oleum, cyclohexanone-oxime is carried out Beckmann rearrangement is known to the skilled person with the reaction process for preparing caprolactam sulfonate, specifically react as follows:
Described oleum refers to well known to a person skilled in the art the sulphuric acid soln of sulphur trioxide.
According to the present invention, the condition of described Beckmann rearrangement can be selected for the routine of this area, generally includes the temperature of reaction and the time of reaction.The temperature of described reaction for example can be 85-130 ℃, and the time of described reaction for example can be 0.1-2 hour.Under preferable case, the temperature of described reaction is 90-120 ℃, and the time of described reaction is 0.5-1 hour.
Further, when described ammonia injects with the form of ammonia, reduced the introducing of water, can avoid like this after reaction finishes, excessive water evaporates the energy consumption that causes by steam heating, be conducive to energy-conservation.
According to the present invention, described neutralization reaction can be carried out in existing various reactors, preferably in and crystal separator in carry out.Described crystal separator preferably includes a plurality of caprolactam sulfonate entrances (being commonly called as the caprolactam sulfonate nozzle) and a plurality of ammonia entrance (being commonly called as the ammonia nozzle).The quantity of described caprolactam sulfonate entrance and ammonia entrance can reasonably be selected according to practical situation, for example, can respectively do for oneself 2-6.Further preferably, a plurality of caprolactam sulfonate entrance is identical with the quantity of a plurality of ammonia entrances; More preferably, a plurality of caprolactam sulfonate entrances and a plurality of ammonia entrance alternative arrangement can make like this material distribute more even and reduce the generation of side reaction.
In addition, the method for hexanolactam provided by the invention and ammonium sulfate coproduction also is included in after neutralization reaction completes, with the product that obtains by settlement separate, with the heavy phase (water) that obtains containing the light phase (oil phase) of hexanolactam and contain ammonium sulfate.Further, light the sending into mutually in follow-up refining step that will contain hexanolactam made with extra care.Contain the heavy phase of ammonium sulfate under the effect of neutralization reaction heat, be that 45-65 ℃, absolute pressure are that 16-20kPa, pH value are carried out evaporation and concentrating under the condition of 4.5-6.5 in temperature, then the concentrate product that obtains is delivered to drying and dehydrating in whizzer, make the export trade of finished product sulfuric acid ammonium packing.Described refining method is known to the skilled person, and will repeat no more at this.
According to the present invention, as shown in Figure 1, the method of hexanolactam provided by the invention and ammonium sulfate coproduction is included under the existence of the vitriol oil, cyclohexanone-oxime is carried out Beckmann rearrangement, obtain containing the product of caprolactam sulfonate, and with this product and ammonia pass into simultaneously be equipped with ammonium sulfate liquor in and carry out neutralization reaction in crystal separator.After neutralization reaction is completed, with the product that obtains by settlement separate, with the heavy phase that obtains containing the light phase of hexanolactam and contain ammonium sulfate.And then light the sending into mutually in follow-up refining step that will contain hexanolactam make with extra care, and obtains the finished product hexanolactam.The heavy phase that contains ammonium sulfate is carried out evaporation and concentrating under the existence of neutralization reaction heat, then the concentrate product that obtains is delivered to drying and dehydrating in whizzer, obtains the finished product sulfuric acid ammonium.
Below will describe the present invention by embodiment.
In following examples and Comparative Examples, the concentration of hexanolactam and the purity of ammonium sulfate all adopt available from the high performance liquid chromatograph of Japanese Shimadzu company and measure.The yield of hexanolactam adopts following formula to calculate with the yield of ammonium sulfate: the theoretical yield of the yield of hexanolactam=(weight of the light concentration of middle hexanolactam mutually * light phase) ÷ hexanolactam * 100%, the theoretical yield of the yield of ammonium sulfate=(purity * weight of ammonium sulfate in product) ÷ ammonium sulfate * 100%.
Embodiment 1
This embodiment is used for illustrating the method for hexanolactam provided by the invention and ammonium sulfate coproduction.
(1) preparation of caprolactam sulfonate:
Be oleum (wherein, the free SO of 104.5 % by weight with cyclohexanone-oxime and concentration
3Content be 20 % by weight) mix according to the ratio of mol ratio 1:1.5, obtain circulation and reset liquid, then the temperature of resetting liquid of circulate introduces in the rearrangement mixing tank after rising to 90 ℃ and reacted 1 hour, obtain containing the solution of caprolactam sulfonate.
(2) coproduction of hexanolactam and ammonium sulfate:
In and crystal separator in advance compound concentration be the ammonium sulfate liquor of 20 % by weight, during its splendid attire liquid level is controlled to be and crystal separator deposit 40% of liquid level.In and crystal separator comprise four caprolactam sulfonate nozzles and four ammonia nozzles, four caprolactam sulfonate nozzles and four ammonia nozzle alternative arrangements.The solution that contains caprolactam sulfonate that step (1) is obtained and ammonia are respectively by during special nozzle passes into separately and crystal separator.Controlling the flow that contains the solution of caprolactam sulfonate in the caprolactam sulfonate nozzle is 7.88m
3/ h, in the ammonia nozzle, ammonia flow is 3130Nm
3/ h.Keep reaction solution in and liquid level in crystal separator be in and crystal separator 40% left and right of depositing liquid level, and in controlling and the temperature in crystal separator be 45 ℃, absolute pressure is 16kPa, the pH value is 5.5.React after 4 hours, reaction product by settlement separate, is obtained containing the light phase and the heavy phase that contains ammonium sulfate of hexanolactam.Wherein, the weight that contains the light phase of hexanolactam is 12.73 tons, and the light concentration of middle hexanolactam mutually is 72.69 % by weight, and yield is 99.93%.The heavy phase that will contain ammonium sulfate is carried out evaporation and concentrating and centrifuge dehydration, and the ammonium sulfate that to obtain 7.63 tons of purity be 99.87 % by weight is premium grads, and yield is 100%.
Embodiment 2
This embodiment is used for illustrating the method for hexanolactam provided by the invention and ammonium sulfate coproduction.
(1) preparation of caprolactam sulfonate:
Identical with embodiment 1.
(2) coproduction of hexanolactam and ammonium sulfate:
In and crystal separator in advance compound concentration be the ammonium sulfate liquor of 20 % by weight, during its splendid attire liquid level is controlled to be and crystal separator deposit 40% of liquid level.In and crystal separator comprise four caprolactam sulfonate nozzles and four ammonia nozzles, four caprolactam sulfonate nozzles and four ammonia nozzle alternative arrangements.The solution that contains caprolactam sulfonate that step (1) is obtained and ammonia are respectively by during special nozzle passes into separately and crystal separator.Controlling the flow that contains the solution of caprolactam sulfonate in the caprolactam sulfonate nozzle is 12.89m
3/ h, in the ammonia nozzle, ammonia flow is 5329Nm
3/ h.Keep reaction solution in and liquid level in crystal separator be in and crystal separator 40% left and right of depositing liquid level, and in controlling and the temperature in crystal separator be 50 ℃, absolute pressure is 18kPa, the pH value is 6.0.React after 2 hours, reaction product by settlement separate, is obtained containing the light phase and the heavy phase that contains ammonium sulfate of hexanolactam.Wherein, the weight that contains the light phase of hexanolactam is 20.75 tons, and the light concentration of middle hexanolactam mutually is 75.42 % by weight, and yield is 99.92%.The heavy phase that will contain ammonium sulfate is carried out evaporation and concentrating and centrifuge dehydration, and the ammonium sulfate that to obtain 12.47 tons of purity be 99.88 % by weight is premium grads, and yield is 100%.
Embodiment 3
This embodiment is used for illustrating the method for hexanolactam provided by the invention and ammonium sulfate coproduction.
(1) preparation of caprolactam sulfonate:
Identical with embodiment 1.
(2) coproduction of hexanolactam and ammonium sulfate:
In and crystal separator in advance compound concentration be the ammonium sulfate liquor of 20 % by weight, during its splendid attire liquid level is controlled to be and crystal separator deposit 40% of liquid level.In and crystal separator comprise four caprolactam sulfonate nozzles and four ammonia nozzles, four caprolactam sulfonate nozzles and four ammonia nozzle alternative arrangements.The solution that contains caprolactam sulfonate that step (1) is obtained and ammonia are respectively by during special nozzle passes into separately and crystal separator.Controlling the flow that contains the solution of caprolactam sulfonate in the caprolactam sulfonate nozzle is 18.32m
3/ h, in the ammonia nozzle, ammonia flow is 7501Nm
3/ h.Keep reaction solution in and liquid level in crystal separator be in and crystal separator 40% left and right of depositing liquid level, and in controlling and the temperature in crystal separator be 65 ℃, absolute pressure is 20kPa, the pH value is 5.9.React after 1 hour, reaction product by settlement separate, is obtained containing the light phase and the heavy phase that contains ammonium sulfate of hexanolactam.Wherein, the weight that contains the light phase of hexanolactam is 29.49 tons, and the light concentration of middle hexanolactam mutually is 76.83 % by weight.The heavy phase that will contain ammonium sulfate is carried out evaporation and concentrating and centrifuge dehydration, and the ammonium sulfate that to obtain 17.75 tons of purity be 99.87 % by weight is premium grads, and yield is 100%.
Embodiment 4
This embodiment is used for illustrating the method for hexanolactam provided by the invention and ammonium sulfate coproduction.
Carry out the preparation of caprolactam sulfonate and the coproduction of hexanolactam and ammonium sulfate according to the method for embodiment 1, different is, the ammonia soln that is 50 % by weight with the equal concentration of mole number with ammonia substitutes, the heavy phase that obtains containing the light phase of hexanolactam and contain ammonium sulfate.Wherein, the weight that contains the light phase of hexanolactam is 14.71 tons, and the light concentration of middle hexanolactam mutually is 62.36 % by weight, and yield is 99.71%.The heavy phase that will contain ammonium sulfate is carried out evaporation and concentrating and centrifuge dehydration, and the ammonium sulfate that to obtain 7.64 tons of purity be 99.76 % by weight is premium grads, and yield is 100%.
Comparative Examples 1
This Comparative Examples is used for the hexanolactam of explanation reference and the method for ammonium sulfate coproduction.
Carry out the preparation of caprolactam sulfonate and the coproduction of hexanolactam and ammonium sulfate according to the method for embodiment 1, different is, in and do not prestore the ammonium sulfate liquor that concentration is 20 % by weight in crystal separator, but the solution that directly will contain caprolactam sulfonate and ammonia respectively by special nozzle separately pass into sky in and crystal separator.React stopped reaction after 4 hours, reaction product by settlement separate, is obtained containing the light phase and the heavy phase that contains ammonium sulfate of hexanolactam.Wherein, the weight that contains the light phase of hexanolactam is 11.65 tons, and the light concentration of middle hexanolactam mutually is 61.08 % by weight, and yield is 76.88%.The heavy phase that will contain ammonium sulfate is carried out evaporation and concentrating and centrifuge dehydration, and the ammonium sulfate that to obtain 6.99 tons of purity be 91.48 % by weight is premium grads, and yield is 83.9%.
As can be seen from the above results, adopt method provided by the invention to carry out the coproduction of hexanolactam and ammonium sulfate, can obtain simultaneously all higher hexanolactam and ammonium sulfate of yield and purity, have prospects for commercial application.Can find out from the contrast of embodiment 1 and 4, when ammonia injects with the form of ammonia, can avoid constantly introducing water in reaction system, thereby not only can reduce system thermal consumption, be conducive to energy-conservation, also help the crystallization of ammonium sulfate, obtain all higher hexanolactam and ammonium sulfate of yield and purity.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove that in addition each the concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. the method for a hexanolactam and ammonium sulfate coproduction, the method comprises: caprolactam sulfonate and ammonia are injected the reactor that is loaded with ammonium sulfate liquor carry out neutralization reaction.
2. method according to claim 1, wherein, described ammonia injects with the form of ammonia.
3. method according to claim 1 and 2, wherein, take the caprolactam sulfonate of 1mol as benchmark, the consumption of described ammonia is 1-3mol.
4. method according to claim 1 and 2, wherein, the condition of described neutralization reaction comprises that temperature is 45-65 ℃, and absolute pressure is 16-20kPa, and the pH value is 4.5-6.5, and the time is 2-10 hour.
5. method according to claim 1, wherein, the concentration of described ammonium sulfate liquor is the 10-40 % by weight.
6. method according to claim 1 or 5, wherein, the splendid attire liquid level of described ammonium sulfate liquor accounts for the 20-50% that described reactor is deposited liquid level.
7. method according to claim 1, wherein, the method also comprises the step for preparing in accordance with the following methods caprolactam sulfonate: under the existence of oleum, cyclohexanone-oxime is carried out Beckmann rearrangement.
8. according to claim 1, the described method of any one in 2,5 and 7, wherein, described reactor comprises a plurality of caprolactam sulfonate entrances and a plurality of ammonia entrance, a plurality of caprolactam sulfonate entrances and a plurality of ammonia entrance alternative arrangement.
9. method according to claim 8, wherein, the quantity of described caprolactam sulfonate entrance and ammonia entrance is respectively done for oneself 2-6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110240495A (en) * | 2019-07-16 | 2019-09-17 | 湖北金湘宁化工科技有限公司 | A kind of method of caprolactam and phosphoric acid coproducing ammonium |
| CN111960894A (en) * | 2020-08-26 | 2020-11-20 | 山西绿丰肥业有限公司 | Water-soluble fertilizer capable of quickly improving nutrients of crops and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108341763B (en) * | 2018-04-24 | 2020-12-01 | 河北美邦工程科技股份有限公司 | Caprolactam crystallization and purification method |
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