CN101121638A - Method for producing mixed butanol and octanol by butanol and octanol residual liquid - Google Patents
Method for producing mixed butanol and octanol by butanol and octanol residual liquid Download PDFInfo
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- CN101121638A CN101121638A CNA2007100163441A CN200710016344A CN101121638A CN 101121638 A CN101121638 A CN 101121638A CN A2007100163441 A CNA2007100163441 A CN A2007100163441A CN 200710016344 A CN200710016344 A CN 200710016344A CN 101121638 A CN101121638 A CN 101121638A
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Abstract
The present invention discloses a method to produce a mixed butanol and octanol using a butanol and octanol residue liquid; the residue liquid is to wipe off the included heavy components through unglued tower first; the hydrogenation material from the tower top is heated to form the mixture gases with material steam and hydrogen in an evaporator; the mixing gases enter the hydrogenation reaction device to make catalyzing and separating; the separated component enters a fractionation unit for product fractionation; the fractionation unit includes butanol tower, middle fractionation tower and octanol tower; the separated component is to reclaim the mixed butanol through the butanol tower; the butanol tower kettle component enters the middle fractionation tower to fraction the middle fractionation, which is to enter the octanol tower to fraction the octanol; the octanol tower kettle component is a high-boiling point solution. The present invention is with simple process to the residue liquid and easy to be operated. The method can produce the high-additional products (mixed with butanol and octanol) in the residue liquid so as to not only decrease the environment pollution but also to enhance the economic benefit.
Description
Technical field
The invention belongs to the treatment technology of chemical enterprise waste residue, particularly a kind of method of utilizing fourth, octanol raffinate to produce mixed butyl alcohol, octanol.
Background technology
The fourth, the octanol raffinate that produce in petroleum chemical enterprise's fourth octanol production process generally are to emit in vain, cause environmental pollution.By analysis, mainly comprise following component in the raffinate:
| Sequence number | Component | Form (wt%) |
| 1 | C8 | 5.0 |
| 2 | C12 | 25.0 |
| 3 | C16 | 60.0 |
| 4 | Heavy constituent | 10.0 |
| Add up to: | 100.0 |
If the C8 in the raffinate, C12, C16 component are recovered utilization, not only can alleviate environmental pollution, and can produce than high value-added product, will have good economic benefits and social benefit.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of utilizing fourth, octanol raffinate to produce mixed butyl alcohol, octanol, and output high value added product from waste residue reduces environmental pollution, increases economic efficiency.
The present invention utilizes fourth, the octanol raffinate is produced mixed butyl alcohol, the method of octanol, it is characterized in that described raffinate at first removes wherein heavy constituent through the matter tower that comes unstuck, the hydrogenating materials of cat head extraction is passed through high temperature with the formation material steam and after hydrogen mixes with the hydrogenating materials of hydrogen mixing cat head extraction in vaporizer in vaporizer, enter hydrogenator with the mixed gas form and carry out catalytic pyrolysis, the cracking component enters fractionation unit and carries out the product fractionation, fractionation unit comprises the butanols tower, middle runnings tower and octanol tower, cracking group is divided through butanols tower recovery mixed butyl alcohol, butanols Tata still component enters the middle runnings tower and fractionates out middle runnings, middle runnings Tata still component enters the octanol tower and fractionates out octanol, and octanol Tata still component is a high boiling solvent.
The present invention to the processing of raffinate through two unit: hydrogenation unit and hydrogenation products fractionation.Hydrogenation unit comprises raw materials pretreatment and two systems of hydrocracking, and the hydrogenation products fractionation unit comprises butanols tower, middle runnings tower and octanol tower three cover distillation systems.In hydrogenation unit, raw material at first removes heavy constituent raffinate to the toxic effect of hydrogenation catalyst through the matter tower that comes unstuck, in vaporizer, mix and the laggard hydrogenator that gasifies then with circulating hydrogen, under catalyst action, under reaction conditionss such as suitable temperature, pressure, the part material generation hydrocracking reaction in the raw material generates reaction product such as butanols, octanol.Reaction product is carried out the recovery of different components by rectifying.
The matter of coming unstuck tower process operational condition: raffinate enters in the tower, and the tower still is heated to 220～245 ℃, and controls the top temperature at 165～185 ℃, tower internal pressure-0.09MPa.The material of extraction is a raffinate at the bottom of the tower, and the material of cat head extraction is a hydrogenating materials.Hydrogenating materials is vapor form by the vaporizer heating and gasifying.
The process conditions of hydrogenator: hydrogenating materials is after heating, be mixed in the reactor with material steam form and hydrogen and react with catalyzer and discharge heat, for reducing temperature, with the thermal oil is that heat-eliminating medium is controlled at 200～228 ℃ with its temperature, and pressure-controlling is at 0.4～0.53MPa.Reactor adopts fixed bed type reactor.The ratio of hydrogenating materials and hydrogen is 1600～1700: 1700～1800 (weight ratios), and hydrogenation catalyst adopts copper-zinc catalyst, and hydrogenating materials spent catalyst consumption per ton is 0.001m
3Hydrogenation catalyst is the HDC-1 type catalyzer of Jiangsu southization group development and production, and mainly chemical composition is, by weight percentage, CuO 30～54%, and ZnO 40～64%, Al2O36-9%.Its technical performance index that reaches is:
Specification: φ 5 * (5.0～5.5) mm
Bulk density: 〉=1.2kg/L
Average radial anti-crushing power: 〉=180N/cm
Radially anti-crushing power is lower than the 120N/cm particle :≤10%
Reaction is after cooling enters the butanols tower and distills, and because of each component boiling point differs, butanols tower still controlled temperature is at 145～152 ℃, and tower top temperature is controlled at 76～85 ℃, in the tower negative pressure be controlled at-0.062～-0.070MPa.The raw material of cat head extraction is a mixed butyl alcohol, and the heavy component of extraction enters the middle runnings tower at the bottom of the tower, and tower still temperature is controlled at 149～155 ℃, and tower top temperature is controlled at 100～113 ℃, in the tower negative pressure be controlled at-0.072～-0.080MPa.Middle runnings column overhead material is middle runnings, enter the octanol tower at the bottom of the tower after the heavy component extraction, tower still temperature is controlled at 176～186 ℃, tower top temperature is controlled at 118～124 ℃, in the tower negative pressure be controlled at-0.08～-0.09MPa, the cat head raw material is an octanol, and the reorganization of extraction is divided into high boiling solvent at the bottom of the tower.
Advantage of the present invention:
Treatment process is simple, and is easy to operate.Can output high value added product (mixed butyl alcohol and octanol) from waste residue, not only reduce environmental pollution but also improved economic benefit.Wherein the yield of mixed butyl alcohol is 28--30%, and the yield of octanol is 5--6%, and the yield of middle runnings is 8--10%, and the yield of high boiling solvent is 20--22%.Middle runnings comprises C5～C7 component, and middle runnings and high boiling solvent can be used for solvent oil, and the purity of the mixed butyl alcohol that obtains is 94--97%, and the purity of octanol is 93--97%, and the purity of middle runnings is 86--90%.
Embodiment
(1) fourth octanol raffinate is through coming unstuck the matter tower, and the function of the matter of coming unstuck tower is the heavy constituent raffinate that removes the toxic effect of hydrogenation catalyst, guarantees carrying out smoothly of follow-up flow process.
(2) the matter tower process operational condition of coming unstuck: raffinate enters in the tower, and inlet amount is 1900kg/h, and the tower still is heated to 220 ℃ (in 220～245 ℃ of scopes all can), and control top temperature is at 170 ℃ (in 165～185 ℃ of scopes all can), tower internal pressure-0.09MPa.The material of extraction is raffinate (190kg/h) at the bottom of the tower, and trim the top of column amount 855kg/h, the material of cat head extraction are hydrogenating materials (produced quantity is 1710kg/h).Hydrogenating materials enters vaporizer, and the effect of vaporizer is that evaporation hydrogenating materials gasification is vapor form, prevents that the objectionable impurities of carrying secretly in the liquid from bringing infringement to hydrogenation catalyst.The temperature of vaporizer is controlled at 100～140 ℃.
(3) process conditions of hydrogenator: hydrogenating materials is after heating, enter in the reactor with the material steam form and to react with catalyzer and discharge heat, for reducing temperature, being heat-eliminating medium with the thermal oil is controlled at 225 ℃ (in 200～228 ℃ of scopes all can) with its temperature, and pressure-controlling is at 0.5MPa (0.4～0.53MPa all can).Hydrogenation catalyst is a copper zinc catalyst of the present invention, as by weight percentage, by CuO 40%, ZnO52%, Al2O38%, perhaps CuO 30%, ZnO 64%, and Al2O3 6%, and perhaps CuO 50%, ZnO 41%, Al2O3 9% etc., hydrogenating materials inlet amount 1677kg/h, circulating hydrogen inlet amount 8000Nm3/h, reactor diameter 2000mm, loaded catalyst 6.0m
3
(4) reaction back end hydrogenation product enters the butanols tower through cooling and distills, because of each component boiling point differs, butanols tower still controlled temperature is at 150 ℃ (145～152 ℃ all can), and tower top temperature is controlled at 81.4 ℃ (76～85 ℃ all can), in the tower negative pressure be controlled at-0.062～-0.070MPa.Inlet amount 1697kg/h, trim the top of column amount 1035kg/h, cat head produced quantity 200.8kg/h is the mixed butyl alcohol component.Produced quantity 1492kg/h at the bottom of the tower, the heavy component of extraction enters the middle runnings tower.Middle runnings Tata still temperature is controlled at 150 ℃ (149～155 ℃ all can), and tower top temperature is controlled at 116.5 ℃ (or 100～113 ℃), in the tower negative pressure be controlled at-0.074MPa (or-0.072～-0.080MPa).Inlet amount 1492kg/h, trim the top of column amount 1450kg/h, cat head produced quantity 140kg/h is middle runnings.Produced quantity 1349kg/h at the bottom of the tower enters the octanol tower after the heavy component extraction of extraction, and tower still temperature is controlled at 181.5 ℃ (or 176～186 ℃), and tower top temperature is controlled at 122.4 ℃ (or 118～124 ℃), in the tower negative pressure be controlled at-0.08～-0.09MPa.Inlet amount 1349kg/h, trim the top of column amount 1975kg/h, cat head produced quantity 784.6kg/h is the octanol component.Produced quantity 562kg/h at the bottom of the tower, the reorganization of extraction is divided into high boiling solvent at the bottom of the tower.
Product yield:
Mixed butyl alcohol 28%
Middle runnings 8%
Octanol 5%
High boiling solvent 20%
Raffinate (heavy constituent) 30%
Product content (purity):
Mixed butyl alcohol 94%
Middle runnings 88%
Octanol 94%
Claims (5)
1. one kind is utilized fourth, the octanol raffinate is produced mixed butyl alcohol, the method of octanol, it is characterized in that described raffinate at first removes wherein heavy constituent through the matter tower that comes unstuck, the hydrogenating materials of cat head extraction is passed through high temperature with the formation material steam and after hydrogen mixes in vaporizer, enter hydrogenator with the mixed gas form and carry out catalytic pyrolysis, the cracking component enters fractionation unit and carries out the product fractionation, fractionation unit comprises the butanols tower, middle runnings tower and octanol tower, cracking group is divided through butanols tower recovery mixed butyl alcohol, butanols Tata still component enters the middle runnings tower and fractionates out middle runnings, middle runnings Tata still component enters the octanol tower and fractionates out octanol, and octanol Tata still component is a high boiling solvent.
2. the method for utilizing fourth, octanol raffinate to produce mixed butyl alcohol, octanol according to claim 1 is characterized in that the tower top temperature that the described matter tower that comes unstuck takes off is controlled at 165～185 ℃, and tower still temperature is 220～245 ℃, and the tower internal pressure is-0.09MPa.
3. the method for utilizing fourth, octanol raffinate to produce mixed butyl alcohol, octanol according to claim 1 is characterized in that the mixed weight ratio of described hydrogenating materials steam and hydrogen is: 1600～1700: 1700～1800.
4. the method for utilizing fourth, octanol raffinate to produce mixed butyl alcohol, octanol according to claim 1, it is characterized in that reaction conditions is in the described hydrogenator: 200～228 ℃ of temperature of reaction, reaction pressure 0.4～0.53MPa, hydrogenation catalyst adopts copper zinc catalyst, its chemical constitution is: by weight percentage, CuO 30～54%, and ZnO 40～64%, Al2O3 6-9%.
5. the fourth of utilizing according to claim 1, the octanol raffinate is produced mixed butyl alcohol, the method of octanol, it is characterized in that described butanols tower, tower still controlled temperature is at 145～152 ℃, tower top temperature is controlled at 76～85 ℃, in the tower negative pressure be controlled at-0.062～-0.070MPa, described middle runnings tower, tower still temperature is controlled at 149～155 ℃, tower top temperature is controlled at 100～113 ℃, in the tower negative pressure be controlled at-0.072～-0.080MPa, described octanol tower, tower still temperature is controlled at 176～186 ℃, tower top temperature is controlled at 118～124 ℃, in the tower negative pressure be controlled at-0.08～-0.09MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710016344A CN100590107C (en) | 2007-07-27 | 2007-07-27 | Method for producing mixed butanol and octanol by butanol and octanol residual liquid |
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| CN200710016344A CN100590107C (en) | 2007-07-27 | 2007-07-27 | Method for producing mixed butanol and octanol by butanol and octanol residual liquid |
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| CN101121638A true CN101121638A (en) | 2008-02-13 |
| CN100590107C CN100590107C (en) | 2010-02-17 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913991A (en) * | 2010-08-20 | 2010-12-15 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| CN103553876A (en) * | 2013-10-23 | 2014-02-05 | 中国海洋石油总公司 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
| CN104151138A (en) * | 2014-08-13 | 2014-11-19 | 中国石油大学(华东) | Process for producing alcohol type high-carbon organic solvent by using n-butanol and n-octanol residual liquid |
| CN106187681A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid front-end hydrogenation low energy consumption |
| CN106187697A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid front-end hydrogenation |
| CN106187699A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid front-end hydrogenation |
| CN106187701A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | Butanol and octanol waste liquid front-end hydrogenation reclaims butanol and the method for capryl alcohol |
| CN106187698A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid back end hydrogenation |
| CN106187700A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid back end hydrogenation |
| CN106187694A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | From butanol and octanol waste liquid, the process for purification of butanol and capryl alcohol is reclaimed by cracking and hydrogenation reaction |
| CN106187693A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The cracking of butanol and octanol waste liquid collection and the separation method of hydrogenation |
| CN110981693A (en) * | 2019-12-25 | 2020-04-10 | 淄博诺奥化工股份有限公司 | Green method for preparing alcohols with high-value of octane by catalytic distillation |
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2007
- 2007-07-27 CN CN200710016344A patent/CN100590107C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913991A (en) * | 2010-08-20 | 2010-12-15 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| CN101913991B (en) * | 2010-08-20 | 2013-03-27 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| CN103553876A (en) * | 2013-10-23 | 2014-02-05 | 中国海洋石油总公司 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
| CN103553876B (en) * | 2013-10-23 | 2014-12-17 | 中国海洋石油总公司 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
| CN104151138A (en) * | 2014-08-13 | 2014-11-19 | 中国石油大学(华东) | Process for producing alcohol type high-carbon organic solvent by using n-butanol and n-octanol residual liquid |
| CN104151138B (en) * | 2014-08-13 | 2016-08-24 | 中国石油大学(华东) | The technique that a kind of octyl alconyl residual liquid produces alcohols high-carbon organic solvent |
| CN106187698A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid back end hydrogenation |
| CN106187693A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The cracking of butanol and octanol waste liquid collection and the separation method of hydrogenation |
| CN106187699A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid front-end hydrogenation |
| CN106187701A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | Butanol and octanol waste liquid front-end hydrogenation reclaims butanol and the method for capryl alcohol |
| CN106187681A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid front-end hydrogenation low energy consumption |
| CN106187700A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid back end hydrogenation |
| CN106187694A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | From butanol and octanol waste liquid, the process for purification of butanol and capryl alcohol is reclaimed by cracking and hydrogenation reaction |
| CN106187697A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid front-end hydrogenation |
| CN106187698B (en) * | 2015-04-29 | 2018-12-28 | 中国石油化工股份有限公司 | The separation and refining method of butanol and octanol waste liquid back end hydrogenation |
| CN106187700B (en) * | 2015-04-29 | 2018-12-28 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid back end hydrogenation |
| CN106187701B (en) * | 2015-04-29 | 2018-12-28 | 中国石油化工股份有限公司 | The method of butanol and octanol waste liquid front-end hydrogenation recycling butanol and octanol |
| CN106187693B (en) * | 2015-04-29 | 2019-02-19 | 中国石油化工股份有限公司 | The cracking of butanol and octanol waste liquid collection and the separation method for adding hydrogen |
| CN106187681B (en) * | 2015-04-29 | 2019-02-19 | 中国石油化工股份有限公司 | The separation method of butanol and octanol waste liquid front-end hydrogenation low energy consumption |
| CN106187694B (en) * | 2015-04-29 | 2019-02-19 | 中国石油化工股份有限公司 | Recycle the refining methd of butanol and octanol from butanol and octanol waste liquid with hydrogenation reaction by cracking |
| CN110981693A (en) * | 2019-12-25 | 2020-04-10 | 淄博诺奥化工股份有限公司 | Green method for preparing alcohols with high-value of octane by catalytic distillation |
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