CN1371906A - Process of distilling residue liquid for recovering and reusing hexanolactam extractant - Google Patents
Process of distilling residue liquid for recovering and reusing hexanolactam extractant Download PDFInfo
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- CN1371906A CN1371906A CN 01106917 CN01106917A CN1371906A CN 1371906 A CN1371906 A CN 1371906A CN 01106917 CN01106917 CN 01106917 CN 01106917 A CN01106917 A CN 01106917A CN 1371906 A CN1371906 A CN 1371906A
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Abstract
The method for recovering and utilizing extractant distillation residue includes the following steps: making reduced pressure distillation of residue, and can obtain the cooled crystal of residue containing caprolactam, organic and inorganic substances from the distilaltion tower, making the obtained crude caprolactan undergo the process of centrifugal separation treatment so as to obtain the caprolastam whose solid content is 90-95 wt%, making reduced pressure distillation to obtain the caprolactam whose solid content is 98-99 wt%. The above-mentioned two kinds of caprolactam can be used for preparing engineering plastics.
Description
The present invention relates to a kind of method of recycling hexanolactam extraction agent vinasse.
Refined caprolactam will extract as extraction agent with a kind of organic solvent, this extraction agent generally has benzene, toluene, chloroform etc., for the quality that guarantees the hexanolactam extraction agent does not influence its effect of extracting, extraction agent need be distilled purification at atmospheric distillation tower, when extraction agent distills Tata still temperature at 100～110 ℃ (when making extraction agent) with benzene, or the extinction value of extraction agent reach 〉=0.1 o'clock, will stop distillation, need the remaining raffinate in distillation tower bottom is drained, add process water and carry out boiling; With yearly capacity is that 50,000 tons hexanolactam device is an example, produces extraction agent vinasse 250～300M
3/ year, it is that 30～40wt%, organic solvent are that 40～55wt%, other impurity are 1～10wt% that this raffinate mainly contains hexanolactam; Present most hexanolactam producer is this raffinate is carried out burning disposal.
The purpose of this invention is to provide a kind of method of recycling hexanolactam extraction agent vinasse.
The present invention be achieved in that with hexanolactam extraction agent vinasse carry out underpressure distillation vacuum meter gauge pressure controlled being made as-0.03～-0.1Mpa, be preferably-0.06～-0.08Mpa, distillation Tata still temperature is 30～150 ℃, preferably should be 40～130 ℃, the light component organism of cat head is at the industrial organic solvent that can be used as, distillation Tata still bottom residues is carried out crystallisation by cooling, Tc-10～40 ℃, carry out then separating with whizzer, but the solid hexanolactam preparation engineering plastics of separating, be particularly suitable for preparing monomer cast nylon, the small amount of liquid that centrifugation is come out is put into receiving tank, carry out underpressure distillation when collecting when a certain amount of, after having distilled, the residue final residuum can be made fuel; Prepare high-quality engineering plastics if desired, just need carry out underpressure distillation to the hexanolactam that centrifugation is come out, improve hexanolactam purity.Concrete processing step is as follows:
1. underpressure distillation raffinate
Hexanolactam extraction agent vinasse is sent into still kettle, vacuumize then, the vacuum meter gauge pressure that keeps still kettle is-0.03～-0.1Mpa between, be preferably-0.06～-0.09Mpa, temperature is controlled to be 40～150 ℃, be preferably 40～130 ℃, the light component organism of cat head is at the industrial solvent that can be used as, and distillation Tata still bottom contains hexanolactam and inorganic, organic residue enters the cooling tank crystallisation by cooling.
2. crystallisation by cooling
Hexanolactam and inorganic, organic residue are contained in the distillation Tata still bottom that enters cooling tank, are-10～40 ℃ of crystallisation by cooling in temperature, obtain crude caprolactam.
3. centrifugation
Crude caprolactam is inserted the whizzer centrifugation, its centrifugal rotational speed is 400～4000 rev/mins, and solid is all separated with liquid, obtains 90～95wt% solid hexanolactam, then this solid hexanolactam is carried out underpressure distillation, the liquid of separating enters receiving tank.
4. underpressure distillation solid hexanolactam
With the solid hexanolactam, be-0.06 in distillation tower vacuum gauge pressure～-0.1Mpa, distillation Tata still temperature is under 120 ℃～170 ℃, underpressure distillation obtains the hexanolactam that purity is 98～99wt%.
5. with purity the hexanolactam preparation engineering plastics of 90～95wt% or 98～99%
With purity is the relevant auxiliary agent of hexanolactam adding of 90～95wt% or 98～99%, the polyreaction that reduces pressure preparation engineering plastics, for monomer cast nylon production, auxiliary agent is a sodium hydroxide etc., temperature of reaction is 120 ℃～140 ℃, and the reaction times is 0.5～1 hour, cast molding, obtain monomer cast nylon, but it is higher to be made into the engineering plastics quality index with step 4.
Positively effect of the present invention is that (1) reduced environmental pollution; (2) 1M
3Extraction agent vinasse raffinate can be created and imitate 4000～8000 yuan; (3) make rational use of resources, reduce the wasting of resources.
Embodiment 1: with 1.5m
3The extraction agent vinasse is sent into distillation tower, in the vacuum gauge pressure be-0.070Mpa under, tower top temperature is 32 ℃, cat head began cut when column bottom temperature was 40 ℃, after 3 hours, tower top temperature is 92 ℃, stops heating during 140 ℃ of end temperature, top discharge is 0.58m
3Organic solvent, the discharging of tower still is 0.86m
3Residue, this residue is put into cooling tank carry out crystallisation by cooling, Tc is 40 ℃, these crystal are sent into whizzer carry out centrifugation, centrifuge speed is 1000 rev/mins, obtain 400 kilograms of white-yellowish solid materials, containing hexanolactam by analysis is 95%, then this hexanolactam being sent into the hexanolactam distillation tower distills, the distillation tower vacuum meter is voltage-controlled to be made as-0.098Mpa, 160 ℃ of tower still temperature controls, steaming hexanolactam is 360 kilograms, caprolactam content is 99.2% by analysis, get 5 kilograms of these hexanolactams and put into polymerization reaction kettle, add 12 gram sodium hydroxide, temperature of reaction is controlled at 140 ℃, reactor vacuum meter pressure-controlled is at-0.098Mpa, reaction times is 45 minutes, be molded in the mould again, detect its 6 mechanical performance index after the moulding and all can be up to state standards, the detection index is: tensile strength is 56.5Mpa, elongation at break is 59.4%, flexural strength is 69.2Mpa, the bending film amount is 1873Mpa, compressive strength 77.7Mpa, notched Izod impact strength 25.5KJ/M
2, heat-drawn wire is 170 ℃, hardness (R scale) 64.6.
Embodiment 2: with 1.5m
3The extraction agent vinasse is sent into distillation tower, in the vacuum gauge pressure be-0.08Mpa under, tower top temperature is 33 ℃, cat head began cut when column bottom temperature was 38 ℃, after 3 hours, tower top temperature is 90 ℃, stops distillation during 139 ℃ of end temperature, top discharge is 0.6m
3Organic solvent, the discharging of tower still is 0.82m
3Residue, this residue is put into cooling tank carry out crystallisation by cooling, Tc is 30 ℃, these crystal are sent into whizzer carry out centrifugation, centrifuge speed is 1200 rev/mins, obtain 406 kilograms of white-yellowish solid materials, containing hexanolactam by analysis is 94.6wt%, then this hexanolactam is sent into the hexanolactam distillation tower and distills, and the distillation tower vacuum meter is voltage-controlled to be made as-0.099Mpa, 160 ℃ of tower still temperature controls, steaming hexanolactam is 363 kilograms, and caprolactam content is 99.1% by analysis, gets 5 kilograms of these hexanolactams and puts into polymerization reaction kettle, add 12 gram sodium hydroxide, temperature of reaction is controlled at 140 ℃, and reactor vacuum meter pressure-controlled was reacted 45 minutes at-0.098Mpa, be molded into again in the mould, detect its 6 mechanical performance index after the moulding and meet the GB requirement; Detect index and be tensile strength and be 52.5Mpa, elongation at break and be 54.4%, flexural strength is that 69Mpa, bending film amount are 1473Mpa, compressive strength 78.7Mpa, notched Izod impact strength 22.5KJ/M
2, heat-drawn wire is 180 ℃, hardness (R scale) 63.6.
Embodiment 3: with 1.5m
3The extraction agent vinasse is sent into distillation tower, is under the 0.078Mpa in the vacuum gauge pressure, and tower top temperature is 33 ℃, and cat head began cut when column bottom temperature was 38 ℃, and after 3 hours, tower top temperature is 90 ℃, stops distillation during 139 ℃ of end temperature, and top discharge is 0.6m
3Organic solvent, the discharging of tower still is 0.82m
3Residue, this residue is put into cooling tank carry out crystallisation by cooling, Tc is 21 ℃, these crystal are sent into whizzer carry out centrifugation, centrifuge speed is 1200 rev/mins, obtain 406 kilograms of white-yellowish solid materials, containing hexanolactam by analysis is 94.6wt%, get 5 kilograms of these hexanolactams and put into polymerization reaction kettle, add 12 gram sodium hydroxide, temperature of reaction is controlled at 140 ℃, reactor vacuum meter pressure-controlled is at-0.098Mpa, reacted 45 minutes, and be molded into again in the mould, detect its 6 mechanical performance index after the moulding and meet the GB requirement; Detect index and be tensile strength and be 50.5Mpa, elongation at break and be 51.4%, flexural strength is that 61Mpa, bending film amount are 1412Mpa, compressive strength 72.7Mpa, notched Izod impact strength 20.5KJ/M
2, heat-drawn wire is 168 ℃, hardness (R scale) 61.6.
Embodiment 4: with 1.5m
3The extraction agent vinasse is sent into distillation tower, in the vacuum gauge pressure be-0.075Mpa under, tower top temperature is 35 ℃, cat head began cut when column bottom temperature was 41 ℃, after 3 hours, tower top temperature is 92 ℃, stops distillation during 145 ℃ of end temperature, top discharge is 0.6m
3Organic solvent, the discharging of tower still is 0.82m
3Residue, this residue is put into cooling tank carry out crystallisation by cooling, Tc is 24 ℃, these crystal are sent into whizzer carry out centrifugation, centrifuge speed is 1500 rev/mins, obtain 401 kilograms of white-yellowish solid materials, containing hexanolactam by analysis is 94.8wt%, get 5 kilograms of these hexanolactams and put into polymerization reaction kettle, add 12 gram sodium hydroxide, temperature of reaction is controlled at 140 ℃, reactor vacuum meter pressure-controlled is at-0.098Mpa, reacted 45 minutes, and be molded into again in the mould, detect its 6 mechanical performance index after the moulding and meet the GB requirement; Detect index and be tensile strength and be 51.2Mpa, elongation at break and be 51.8%, flexural strength is that 62Mpa, bending film amount are 1434Mpa, compressive strength 72.9Mpa, notched Izod impact strength 21.5KJ/M
2, heat-drawn wire is 171 ℃, hardness (R scale) 62.
Claims (1)
1. method of recycling the extraction agent vinasse is characterized in that may further comprise the steps:
(1) underpressure distillation raffinate
Hexanolactam extraction agent vinasse is sent into still kettle, the vacuum meter gauge pressure that keeps still kettle is-0.03～-0.1Mpa between, be preferably-0.06～-0.09Mpa, temperature is controlled to be 30～150 ℃, be preferably 40～130 ℃, the light component organism of cat head is at the industrial solvent that can be used as, and distillation Tata still bottom contains hexanolactam and inorganic, organic residue enters the cooling tank crystallisation by cooling, then
(2) crystallisation by cooling
Hexanolactam and inorganic, organic residue are contained in the distillation Tata still bottom that enters cooling tank, are-10～40 ℃ of crystallisation by cooling in temperature, obtain crude caprolactam, then
(3) centrifugation
Crude caprolactam is inserted the whizzer centrifugation, and its centrifugal rotational speed is 400～4000 rev/mins, and solid is all separated with liquid, obtain 90～95wt% solid hexanolactam, then this solid hexanolactam is carried out underpressure distillation, the liquid of separating enters receiving tank, then
(4) underpressure distillation solid hexanolactam
With the solid hexanolactam, be-0.06 in distillation tower vacuum gauge pressure～-0.1Mpa, distillation Tata still temperature is under 120 ℃～170 ℃, underpressure distillation obtains the hexanolactam that purity is 98～99wt%, then
(5) with purity be the hexanolactam preparation engineering plastics of 90～95wt% or 98～99%
With purity is the relevant auxiliary agent of hexanolactam adding of 90～95wt% or 98～99%, the polyreaction that reduces pressure preparation engineering plastics, for monomer cast nylon production, auxiliary agent is a sodium hydroxide etc., temperature of reaction is 120 ℃～160 ℃, reaction times is 0.5～1 hour, and cast molding obtains monomer cast nylon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01106917 CN1371906A (en) | 2001-02-28 | 2001-02-28 | Process of distilling residue liquid for recovering and reusing hexanolactam extractant |
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| CN 01106917 CN1371906A (en) | 2001-02-28 | 2001-02-28 | Process of distilling residue liquid for recovering and reusing hexanolactam extractant |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352034A (en) * | 2011-07-22 | 2012-02-15 | 浙江华建尼龙有限公司 | Mechanical method and apparatus for removing polycarprolactam dimers |
| CN102391064A (en) * | 2011-09-19 | 2012-03-28 | 湖南百利工程科技有限公司 | Process for recovering and refining extracting agent in production procedure of hexanolactam |
| CN103539738A (en) * | 2013-11-01 | 2014-01-29 | 华东理工大学 | Method and device for recovering caprolactam in benzene distillation residue |
| CN105683161A (en) * | 2013-07-09 | 2016-06-15 | 德希尼布吉玛股份有限公司 | Process for the recovery of epsilon-caprolactam from extract water |
| CN107778244A (en) * | 2017-12-07 | 2018-03-09 | 陕西科原环保节能科技有限公司 | A kind of method of refined purification caprolactam |
| CN108946850A (en) * | 2018-08-14 | 2018-12-07 | 河北蓝江生物环保科技有限公司 | Evaporate the Retreatment method of raffinate |
| CN110092754A (en) * | 2019-05-23 | 2019-08-06 | 河北美邦工程科技股份有限公司 | A kind of polishing purification method of caprolactam vinasse |
| CN111039869A (en) * | 2020-01-16 | 2020-04-21 | 河北美邦工程科技股份有限公司 | Treatment method of caprolactam benzene distillation residual liquid |
| CN111138362A (en) * | 2020-01-13 | 2020-05-12 | 福建永荣科技有限公司 | Method for treating crude benzene distillation raffinate in caprolactam refining process |
| CN112174423A (en) * | 2019-10-11 | 2021-01-05 | 福建天辰耀隆新材料有限公司 | Method for treating caprolactam production wastewater |
-
2001
- 2001-02-28 CN CN 01106917 patent/CN1371906A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352034A (en) * | 2011-07-22 | 2012-02-15 | 浙江华建尼龙有限公司 | Mechanical method and apparatus for removing polycarprolactam dimers |
| CN102352034B (en) * | 2011-07-22 | 2013-01-30 | 浙江华建尼龙有限公司 | Mechanical method and apparatus for removing polycarprolactam dimers |
| CN102391064A (en) * | 2011-09-19 | 2012-03-28 | 湖南百利工程科技有限公司 | Process for recovering and refining extracting agent in production procedure of hexanolactam |
| CN102391064B (en) * | 2011-09-19 | 2013-08-14 | 湖南百利工程科技股份有限公司 | Process for recovering and refining extracting agent in production procedure of hexanolactam |
| CN105683161A (en) * | 2013-07-09 | 2016-06-15 | 德希尼布吉玛股份有限公司 | Process for the recovery of epsilon-caprolactam from extract water |
| CN103539738A (en) * | 2013-11-01 | 2014-01-29 | 华东理工大学 | Method and device for recovering caprolactam in benzene distillation residue |
| CN104326982A (en) * | 2013-11-01 | 2015-02-04 | 华东理工大学 | Method and device for recycling caprolactam in benzene distillation residual liquid |
| CN104326982B (en) * | 2013-11-01 | 2017-01-18 | 华东理工大学 | Method and device for recycling caprolactam in benzene distillation residual liquid |
| CN107778244A (en) * | 2017-12-07 | 2018-03-09 | 陕西科原环保节能科技有限公司 | A kind of method of refined purification caprolactam |
| CN107778244B (en) * | 2017-12-07 | 2021-03-16 | 陕西科原环保节能科技有限公司 | Method for refining and purifying caprolactam |
| CN108946850A (en) * | 2018-08-14 | 2018-12-07 | 河北蓝江生物环保科技有限公司 | Evaporate the Retreatment method of raffinate |
| CN108946850B (en) * | 2018-08-14 | 2021-07-16 | 河北蓝江生物环保科技有限公司 | Method for reprocessing evaporation raffinate |
| CN110092754A (en) * | 2019-05-23 | 2019-08-06 | 河北美邦工程科技股份有限公司 | A kind of polishing purification method of caprolactam vinasse |
| CN112174423A (en) * | 2019-10-11 | 2021-01-05 | 福建天辰耀隆新材料有限公司 | Method for treating caprolactam production wastewater |
| CN111138362A (en) * | 2020-01-13 | 2020-05-12 | 福建永荣科技有限公司 | Method for treating crude benzene distillation raffinate in caprolactam refining process |
| CN111039869A (en) * | 2020-01-16 | 2020-04-21 | 河北美邦工程科技股份有限公司 | Treatment method of caprolactam benzene distillation residual liquid |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: BALIN BRANCH CORP. SINOPEC Effective date: 20050107 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20050107 Address after: 6, Yi Xin East Street, Beijing, Chaoyang District Applicant after: Sinopec Corp. Address before: 414000 No. 29 Nanhu Avenue, Hunan, Yueyang Applicant before: Baling Branch, China Petro-Chemical Co., Ltd. |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |