CN113735688A - Recycling method of waste liquid of butanol device - Google Patents
Recycling method of waste liquid of butanol device Download PDFInfo
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- CN113735688A CN113735688A CN202111031418.5A CN202111031418A CN113735688A CN 113735688 A CN113735688 A CN 113735688A CN 202111031418 A CN202111031418 A CN 202111031418A CN 113735688 A CN113735688 A CN 113735688A
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only
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Abstract
The invention discloses a method for recycling waste liquid of a butanol device, which comprises the following steps: a. pretreating the waste liquid of the butanol device by ion exchange resin filled in a fixed bed; b. pressurizing the pretreated waste liquid, fully mixing the pretreated waste liquid with high-pressure hydrogen in a static mixer, and feeding the mixture into a fixed bed reactor for hydrogenation reaction; a hydrogenation catalyst is filled in the fixed bed reactor; c. after the reaction is finished, removing hydrogen and other light components dissolved in the reaction liquid through a high-pressure degassing tank; d. and (4) sending the degassed reaction liquid to a product refining tower, and rectifying and separating to obtain the butanol. The invention provides a resource recycling method aiming at the specific composition of the waste liquid of the butanol device, and the resource recycling method has the advantages of high ester conversion rate, high product selectivity and long service life of the catalyst.
Description
Technical Field
The invention relates to a recycling method, in particular to a recycling method of waste liquid of a butanol device.
Background
In the existing industrial process for preparing butanol, there are mainly two main process technologies: homogeneous hydroformylation reaction technology and aqueous hydroformylation reaction technology. The homogeneous phase hydroformylation reaction technology has a relatively wider application range, and takes a rhodium metal complex as a catalyst to cause the synthesis gas and the propylene to carry out carbonylation reaction to generate butyraldehyde, and the butyraldehyde is further hydrogenated to produce the butanol.
Heavy components are generated in the carbonylation reaction and the butyraldehyde hydrogenation process, and the waste liquid of a butanol production device can contain 10-15% of butyraldehyde, 1-2% of butyric acid, 5-10% of butanol, 50-60% of ester impurities and 20-30% of carbon twelve and above substances. At present, the heavy component is complex in components, high in comprehensive recycling difficulty and low in investment return rate, basically adopts incineration as a main treatment mode, greatly wastes energy and is not beneficial to reducing carbon emission.
Patent CN101973846B discloses a method for producing mixed butanol and crude octanol by using waste liquid of butanol and octanol device as raw material, which comprises separating butyraldehyde, butanol, and carbon eight components by fractionation device, hydrogenating aldehydes to generate butanol and octanol, and obtaining high-purity butanol and octanol by complex rectification system. The process flow is relatively long, the number of the rectifying towers used for raw material fractionation and product refining is relatively large, and the investment is huge.
Patent CN112321386A discloses a method for hydrotreating butanol-octanol waste liquid, which uses organic base as alkaline auxiliary agent, then carries out catalytic hydrogenation conversion at 230-280 ℃ to separate and obtain alcohol products. However, the method is not suitable for the waste liquid of the butanol production device provided by the invention, and the following three reasons are mainly provided: firstly, the butyl alcohol waste liquid has higher ester content, but the ester substance is difficult to convert under the conventional hydrogenation catalyst and catalysis condition, and the patent experiment data does not show the conversion data of the ester; secondly, the hydrogenation conditions in the method are harsh, the hydrogenation temperature above 230 ℃ is required, a large amount of aldehydes in the butanol waste liquid can be subjected to condensation cyclization at a high temperature to generate trioxane polymers, so that the recovery of valuable components is not facilitated, and the quality of recovered products can be influenced; thirdly, under the condition of the scheme, the service life of the catalyst is short, and the long-period stable operation of the device cannot be ensured.
Disclosure of Invention
In order to solve the technical problems, the invention provides a resource recycling method aiming at the specific composition of the waste liquid of the butanol device, and the method can shorten the process flow, reduce the equipment investment, prolong the service life of the catalyst, realize the high ester conversion rate, maximally realize the effect of recycling useful components and obviously improve the atom economy.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for recycling waste liquid of a butanol device comprises the following steps:
a. pretreating butanol device waste liquid through ion exchange resin filled in a fixed bed so as to control metal ions in the waste liquid to be below 1 ppm;
b. pressurizing the pretreated waste liquid by a booster pump, preferably 3-8MPa of the outlet pressure of the booster pump, fully mixing the waste liquid with high-pressure hydrogen in a static mixer, feeding the mixture into a fixed bed reactor for hydrogenation reaction, and hydrogenating aldehyde, acid and ester substances in the waste liquid to convert the aldehyde, acid and ester substances into alcohol; a hydrogenation catalyst is filled in the fixed bed reactor;
c. after the reaction is finished, removing hydrogen and other light components dissolved in the reaction liquid through a high-pressure degassing tank;
d. and (4) sending the degassed reaction liquid to a product refining tower, and rectifying and separating to obtain the butanol.
According to the invention, researches unexpectedly find that metal ions (generated by corrosion of a device) in the waste liquid are controlled below 1ppm by means of pretreatment of ion exchange resin, and then aldehyde, acid and ester in the waste liquid are subjected to hydrogenation reaction by a Cu/Al/Zn catalyst, especially butyl butyrate is converted into butanol, so that butanol can be recovered with high selectivity, the catalyst has long service life and good product quality, long-period stable operation of the device is maintained, and the catalyst cost and the production cost are reduced, thereby greatly improving the economic benefit.
Preferably, the butanol plant waste stream comprises the following content ranges of components: 10-15% of butyraldehyde, 1-2% of butyric acid, 5-10% of butanol, 50-60% of esters, and 20-30% of carbon twelve and above substances. For the butanol device waste liquid containing higher esters, the method can still convert the esters into butanol by hydrogenation with high conversion rate, thereby improving the product yield.
In a preferred embodiment of the invention, the ion exchange resin is an ion exchange resin having sulfonic acid functional groups, preferably one or more of LX-160, LX-36 and LSC-485 as known in the name of seian blue.
In a preferred embodiment of the invention, the operating pressure in step a is from 45 to 50kpa gauge pressure, the operating temperature is from 30 to 90 ℃, preferably from 40 to 50 ℃, and the space velocity is from 1 to 1.5h-1。
In a preferred embodiment of the present invention, the hydrogenation catalyst is a catalyst containing one or more of metal copper, aluminum, zinc, cobalt, nickel; preferably, the hydrogenation catalyst is a mixture containing metal copper, aluminum and zinc in a molar ratio of (0.8-1.3) to 1 (0.1-0.3).
The hydrogenation catalyst may be prepared by a coprecipitation method as follows:
dissolving metal precursors of copper, aluminum and zinc in water to prepare a mixed solution, dropwise adding the mixed solution into a dispersion liquid of nano titanium dioxide, and dropwise adding an alkaline precipitator to perform coprecipitation reaction; controlling the pH value of the system to be 5-9 in the reaction process, adjusting the pH value to be 8-10 after the reaction is finished, and aging to obtain slurry; and taking solid from the filtered slurry, washing the solid by deionized water, drying the washed solid, and roasting the dried solid at the temperature of 500-800 ℃ for 4-24 hours to obtain the hydrogenation catalyst.
The nano titanium dioxide is used for inducing the metal precursor to precipitate into a compact structure and increasing the strength, and the using amount of the nano titanium dioxide is 3-5% of the total molar amount of metal Cu/Al/Zn.
The alkaline precipitator is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate and ammonia water.
In a preferred embodiment of the present invention, the hydrogenation reaction conditions in step b are that the operation pressure is 4-6MPa gauge pressure, the operation temperature is 160-220 ℃, preferably 180-200 ℃.
Under the hydrogenation condition of the invention, the reaction condition is mild, not only can higher catalytic activity be realized, but also the aldehyde substance can be stabilized to be more prone to generate butanol rather than a condensation product, thereby improving the product selectivity.
In a preferred embodiment of the invention, the space velocity of the feed for the hydrogenation in step b is between 0.5 and 3h-1Preferably 1-2h-1。
Preferably, the fixed bed reactor is provided with an external recycle stream, and the heat of hydrogenation reaction is removed by circulating water.
In a preferred embodiment of the invention, the feed end of the static mixer in the step b is provided with a feed buffer tank, and the discharge port at the bottom of the feed buffer tank is provided with a metal wire wound filter so as to remove solid particles carried in the waste liquid before the waste liquid enters the fixed bed reactor and avoid poisoning the hydrogenation catalyst;
preferably, the feed buffer tank is operated at a pressure of 40 to 50KPa gauge and at a temperature of 35 to 40 ℃.
In a preferred embodiment of the invention, the top of the high pressure degassing tank is provided with a demister to reduce liquid phase entrainment in the gas phase;
preferably, the operating conditions of the high-pressure degassing tank are an operating pressure gauge pressure of 90-100kpa and an operating temperature of 40-50 ℃.
In a preferred embodiment of the invention, butanol is extracted from the side line of the product refining tower in the step d, non-condensable gas discharged from the top of the tower is returned to a butanol device for recycling, and heavy components are removed from the bottom of the tower.
In a preferred embodiment of the present invention, the rectification separation conditions in step d are: the operation pressure gauge pressure at the top of the tower is 10-15kpa, the operation temperature is 110-; the operating pressure gauge pressure of the tower kettle is 35-40kpa, and the operating temperature is 135-; the side stream operation temperature is 123-125 ℃, and the side stream extraction product is mainly butanol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method is characterized in that hydrogenation reaction condition design and optimization are carried out according to the characteristics and specific composition of the waste liquid of the butanol device, a series of operations including raw material pretreatment and the like are carried out, finally, high conversion rate of aldehyde, acid and ester in the waste liquid and high selectivity of n-isobutanol are realized, the economy of the device can be effectively improved, and carbon emission is reduced.
(2) The method has the advantages that the waste liquid of the ion exchange resin kettle is pretreated before hydrogenation reaction, metal ions in the waste liquid are controlled to be below 1ppm, the service life of a catalyst is unexpectedly found to be prolonged, and the long-period stable operation of the device can be ensured.
(3) The hydrogenation reaction condition temperature is lower, which is beneficial to stabilizing aldehyde substances and leading the aldehyde substances to be more prone to generating butanol rather than condensation products, thereby improving the product selectivity.
(4) The metal wire wound filter is arranged at the discharge port at the bottom of the feeding buffer tank, so that solid particles carried in the waste liquid are removed before the waste liquid enters the fixed bed reactor, the hydrogenation catalyst is prevented from being poisoned, the catalytic activity of the catalyst is ensured in all aspects and conditions, and the catalytic efficiency is ensured.
(5) The device adopted by the process can be linked with a butanol production device, and tail gas removed from the high-pressure degassing tank and noncondensable gas (main component hydrogen) of the product refining tower can return to the butanol production device for the procedure of producing butanol by hydrogenating butyraldehyde, so that gas phase recycling is realized.
Drawings
FIG. 1 is an overall process flow diagram of example 1.
Detailed Description
The invention is further illustrated by the accompanying drawings and specific examples, which are given by way of illustration only and do not limit the scope of the invention.
In the embodiment, an Agilent chromatographic analysis is adopted as a positive-to-differential ratio analysis method, and the specific determination method comprises the following steps:
sample introduction amount: 0.2 mu L; column temperature: keeping the temperature at 50 ℃ for 4min, heating to 60 ℃ at 3 ℃/min, heating to 150 ℃ at 10 ℃/min, heating to 230 ℃ at 20 ℃/min, and keeping the temperature for 8 min; sample inlet temperature: at 250 ℃ to obtain a mixture.
Flow rate of spacer purge gas: 3.0 mL/min; flow rate of chromatography column (N)2):1 mL/min; split-flow sample injection with a split-flow ratio of 30: 1; a detector: 280 ℃; hydrogen flow rate: 30 mL/min; air flow rate: 400 mL/min; tail gas blowing flow: 25 mL/min.
The butanol plant waste liquid employed in each example and comparative example was from a wanhua chemical butanol plant and consisted of: 1% of butyric acid, 10% of n-butyraldehyde, 6% of n-butanol, 60% of butyl butyrate, 23% of heavy components and 40ppm of metal ions (wherein the iron ions are 24ppm, the chromium ions are 12ppm and the nickel ions are 4 ppm).
In the examples of the present invention, the reaction pressure conditions were gauge pressures unless otherwise specified.
Preparation of catalyst A [ preparation example 1 ]
3kg of deionized water is added into the reaction kettle, 11.7g of nano titanium dioxide with the particle size of 20-30nm is added, and the mixture is stirred uniformly.
Dissolving 270.2g of anhydrous copper nitrate, 631.2g of aluminum nitrate nonahydrate and 65.8g of zinc nitrate hexahydrate in 2.5kg of deionized water to prepare a metal mixed solution; in addition, 20% sodium carbonate solution is prepared in sufficient quantity; heating the metal mixed solution and the sodium carbonate solution to 80 ℃, simultaneously dropwise adding the metal mixed solution and the sodium carbonate solution into a reaction kettle for coprecipitation reaction, controlling the temperature of the reaction kettle to be constant at 80 ℃, controlling the dropwise adding amount of the sodium carbonate solution in the dropwise adding process, maintaining the pH value of the system to be 5-6, and finishing dropwise adding the metal mixed solution within 1.5 h. And adjusting the pH value of the system to 9 by adopting the sodium carbonate solution, and aging for 3 h.
Then filtering, washing, drying the filter cake at 120 ℃ for 24h, roasting at 600 ℃ for 5h, crushing and pressing the roasted filter cake, and cutting the filter cake into strip-shaped catalysts with the diameter of 5mm and the length of 10mm to obtain the catalyst A. Before use, the catalyst is reduced by hydrogen for 12h at 500 ℃, the operation pressure gauge pressure is 10kpa, and the space velocity is 500h-1。
Preparation of catalyst B [ preparation example 2 ]
3kg of deionized water is added into the reaction kettle, 11.7g of nano titanium dioxide with the particle size of 20-30nm is added, and the mixture is stirred uniformly.
272.8g of anhydrous copper nitrate, 630.5g of aluminum nitrate nonahydrate and 133.1g of zinc nitrate hexahydrate are dissolved in 2.5kg of deionized water to prepare a metal mixed solution. Additionally preparing sufficient 20 wt% sodium carbonate solution; heating the metal mixed solution and the sodium carbonate solution to 80 ℃, simultaneously dropwise adding the metal mixed solution and the sodium carbonate solution into a reaction kettle for coprecipitation reaction, controlling the temperature of the reaction kettle to be constant at 80 ℃, controlling the dropwise adding amount of the sodium carbonate solution in the dropwise adding process, maintaining the pH value of the system to be 5-6, and finishing dropwise adding the mixed solution within 1.5 h. And adjusting the pH value of the system to 9 by adopting the sodium carbonate solution, and aging for 3 h.
And then filtering, washing, drying the filter cake at 120 ℃ for 24h, roasting at 600 ℃ for 5h, crushing and pressing the roasted filter cake, and cutting the filter cake into strip-shaped catalysts with the diameter of 5mm and the length of 10mm to obtain the catalyst B. Before use, the catalyst is reduced by hydrogen for 12h at 500 ℃, the operation pressure gauge pressure is 10kpa, and the space velocity is 500h-1。
Preparation of catalyst C [ preparation example 3 ]
3kg of deionized water is added into the reaction kettle, 11.7g of nano titanium dioxide with the particle size of 20-30nm is added, and the mixture is stirred uniformly.
408.6g of anhydrous copper nitrate, 629.6g of aluminum nitrate nonahydrate and 66.3g of zinc nitrate hexahydrate are dissolved in 2.5kg of deionized water to prepare a metal mixed solution; and additionally, enough 20 wt% of sodium carbonate solution is prepared, the metal mixed solution and the sodium carbonate solution are heated to 80 ℃, and are simultaneously dripped into a reaction kettle for coprecipitation reaction, the temperature of the reaction kettle is controlled to be constant at 80 ℃, the dripping amount of the sodium carbonate is controlled in the dripping process, the pH value of the system is maintained at 5-6, and the dripping of the mixed solution is finished within 1.5 h. And adjusting the pH value of the system to 9 by adopting the sodium carbonate solution, and aging for 3 h.
And then filtering, washing, drying the filter cake at 120 ℃ for 24h, roasting at 600 ℃ for 5h, crushing and pressing the roasted filter cake, and cutting the filter cake into strip-shaped catalysts with the diameter of 5mm and the length of 10mm to obtain the catalyst C. Before use, the catalyst is reduced by hydrogen for 12h at 500 ℃, the operation pressure gauge pressure is 10kpa, and the space velocity is 500h-1。
Preparation of catalyst D [ preparation example 4 ]
3kg of deionized water is added into the reaction kettle, 11.7g of nano titanium dioxide with the particle size of 20-30nm is added, and the mixture is stirred uniformly.
Dissolving 409.2g of anhydrous copper nitrate, 630.8g of aluminum nitrate nonahydrate and 133.3g of zinc nitrate hexahydrate in 2.5kg of deionized water to prepare a metal mixed solution; a 20 wt% sodium carbonate solution was additionally prepared and both the metal mixed solution and the sodium carbonate solution were heated to 80 ℃. And simultaneously dropwise adding the mixed solution into a reaction kettle for coprecipitation reaction, controlling the temperature of the reaction kettle to be constant at 80 ℃, controlling the dropping amount of sodium carbonate in the dropwise adding process, maintaining the pH of the system to be 5-6, and finishing dropwise adding the mixed solution within 1.5 h. And adjusting the pH value of the system to 9 by adopting the sodium carbonate solution, and aging for 3 h.
And then filtering, washing, drying the filter cake at 120 ℃ for 24h, roasting at 600 ℃ for 5h, crushing and pressing the roasted filter cake, and cutting the filter cake into strip-shaped catalysts with the diameter of 5mm and the length of 10mm to obtain the catalyst D. Before use, the catalyst is reduced by hydrogen for 12h at 500 ℃, the operation pressure gauge pressure is 10kpa, and the space velocity is 500h-1。
Preparation of catalyst E [ preparation example 5 ]
3kg of deionized water is added into the reaction kettle, 11.7g of nano titanium dioxide with the particle size of 20-30nm is added, and the mixture is stirred uniformly.
305.5g of anhydrous copper nitrate, 631g of aluminum nitrate nonahydrate and 92.4g of zinc nitrate hexahydrate are dissolved in 2.5kg of deionized water to prepare a metal mixed solution; and additionally, enough 20 wt% of sodium carbonate solution is prepared, the metal mixed solution and the sodium carbonate solution are heated to 80 ℃, and are simultaneously dripped into a reaction kettle for coprecipitation reaction, the temperature of the reaction kettle is controlled to be constant at 80 ℃, the dripping amount of the sodium carbonate is controlled in the dripping process, the pH value of the system is maintained at 5-6, and the dripping of the mixed solution is finished within 1.5 h. And adjusting the pH value of the system to 9 by adopting the sodium carbonate solution, and aging for 3 h.
Then filtering, washing, drying the filter cake at 120 ℃ for 24h, roasting at 600 ℃ for 5h, crushing and pressing the roasted filter cake, and cutting the filter cake into strip-shaped catalysts with the diameter of 5mm and the length of 10mm to obtain the catalyst E. Before use, the catalyst is reduced by hydrogen for 12h at 500 ℃, the operation pressure gauge pressure is 10kpa, and the space velocity is 500h-1。
Preparation of catalyst F [ preparation example 6 ]
3kg of deionized water is added into the reaction kettle, 11.7g of nano titanium dioxide with the particle size of 20-30nm is added, and the mixture is stirred uniformly.
374.5g of anhydrous copper nitrate, 631g of aluminum nitrate nonahydrate and 105.4g of zinc nitrate hexahydrate are dissolved in 2.5kg of deionized water to prepare a metal mixed solution; and additionally, enough 20 wt% of sodium carbonate solution is prepared, the metal mixed solution and the sodium carbonate solution are heated to 80 ℃, and are simultaneously dripped into a reaction kettle for coprecipitation reaction, the temperature of the reaction kettle is controlled to be constant at 80 ℃, the dripping amount of the sodium carbonate is controlled in the dripping process, the pH value of the system is maintained at 5-6, and the dripping of the mixed solution is finished within 1.5 h. And adjusting the pH value of the system to 9 by adopting the sodium carbonate solution, and aging for 3 h.
And then filtering, washing, drying the filter cake at 120 ℃ for 24h, roasting at 600 ℃ for 5h, crushing and pressing the roasted filter cake, and cutting the filter cake into strip-shaped catalysts with the diameter of 5mm and the length of 10mm to obtain the catalyst F. Before use, the catalyst is reduced by hydrogen for 12h at 500 ℃, the operation pressure gauge pressure is 10kpa, and the space velocity is 500h-1。
[ example 1 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid passes through ion exchange resin (Xian lan Xiao LX-160) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1h-1. Testing the content of metal ions in the pretreated waste liquid to be 0.5 ppm;
(2) enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 1h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 100kpa, and the operating temperature is 50 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 10kpa, the operation temperature is 110 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 35kpa, and the operation temperature is 135 ℃; the side line operation temperature is 123 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 2 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid passes through ion exchange resin (Xian lan Xiao LX-160) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1.5h-1. Testing the content of metal ions in the pretreated waste liquid to be 0.1 ppm;
(2) enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operation temperature of 45 ℃ and the operation pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 1.5h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 100kpa, and the operating temperature is 40 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 3 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid passes through ion exchange resin (Xian lan Xiao LX-36) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 45kpa, and the liquid hourly space velocity is 1h-1. Testing the content of metal ions in the pretreated waste liquid to be 0.4 ppm;
(2) enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 45kpa, and then sending the waste liquid into a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 2.0h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 90kpa, and the operating temperature is 50 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 4 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid passes through ion exchange resin (Xian lan Xiao LX-36) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 50 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1h-1. Testing the content of metal ions in the pretreated waste liquid to be 0.2 ppm;
(2) enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 3h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 90kpa, and the operating temperature is 40 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 5 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid is passed through ion exchange resin (LSC-485 in Xian blue) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1h-1. And metal ions in the pretreated waste liquid are not detected.
(2) Enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 160 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 1.5h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 100kpa, and the operating temperature is 50 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 6 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid passes through ion exchange resin (Xian lan Xiao LX-160) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1h-1. And metal ions in the pretreated waste liquid are not detected.
(2) Enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 180 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 1.5h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 100kpa, and the operating temperature is 50 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 7 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid passes through ion exchange resin (Xian lan Xiao LX-36) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1h-1. Testing the content of metal ions in the pretreated waste liquid to be 0.6 ppm;
(2) enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 200 ℃, the reaction pressure is 4MPa, and the liquid hourly space velocity is 1.5h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 100kpa, and the operating temperature is 50 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 8 ]
Recycling waste liquid of the butanol device according to the process flow shown in figure 1:
(1) the butanol device waste liquid is passed through ion exchange resin (LSC-485 in Xian blue) to remove metal ions, and the operation conditions are as follows: the filling amount of the resin column is 30ml, the height-diameter ratio of the bed layer is 2:1, the temperature is 40 ℃, the pressure is 50kpa, and the liquid hourly space velocity is 1h-1. Testing the content of metal ions in the pretreated waste liquid to be 0.1 ppm;
(2) enabling the pretreated waste liquid to pass through a feeding buffer tank, filtering to remove solid particles through a metal wire wound filter at the bottom of the tank at the operating temperature of 40 ℃ and the operating pressure of 40kpa, and then sending the waste liquid to a static mixer to be efficiently mixed with hydrogen;
(3) delivering the efficiently mixed waste liquid and hydrogen to a hydrogenation reactor for hydrogenation reaction, wherein the loading amount of a hydrogenation catalyst E is 30ml, the height-diameter ratio of a bed layer is 2:1, the reaction temperature is 200 ℃, the reaction pressure is 6MPa, and the liquid hourly space velocity is 1.5h-1And the molar flow ratio of the hydrogen to the waste liquid is 2: 1.
(4) Feeding the solution from the hydrogenation reactor into a high-pressure degassing tank for degassing, and controlling the operation conditions as follows: the operating pressure is 100kpa, and the operating temperature is 50 ℃;
(5) and (3) conveying the solution from the high-pressure degassing tank to a refining tower for rectification and separation of products, wherein the operating conditions of the refining tower are as follows: the operation pressure at the top of the tower is 15kpa, the operation temperature is 120 ℃, and the liquid phase is subjected to total reflux; the operation pressure of the tower kettle is 40kpa, and the operation temperature is 140 ℃; the side line operating temperature is 125 ℃, and the product butanol is extracted from the side line.
In the above process, a sample at the outlet of the hydrogenation reactor was taken for component testing, and the conversion rates of aldehyde, acid and ester and the selectivity of butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 9 ]
The butanol plant waste stream was recycled as in example 2, except that the hydrogenation catalyst in step (3) was the catalyst a prepared in the preceding preparatory example.
A sample at the outlet of the hydrogenation reactor was taken for composition testing, and the conversion of aldehyde, acid, ester and selectivity to butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 10 ]
The butanol plant waste stream was recycled as in example 2, except that the hydrogenation catalyst in step (3) was the catalyst B prepared in the previous preparation example.
A sample at the outlet of the hydrogenation reactor was taken for composition testing, and the conversion of aldehyde, acid, ester and selectivity to butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 11 ]
The butanol plant waste stream was recycled as in example 2, except that catalyst C prepared in the preceding preparatory example was used as the hydrogenation catalyst in step (3).
A sample at the outlet of the hydrogenation reactor was taken for composition testing, and the conversion of aldehyde, acid, ester and selectivity to butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 12 ]
The butanol plant waste stream was recycled as in example 2, except that the hydrogenation catalyst in step (3) was the catalyst D prepared in the preceding preparatory example.
A sample at the outlet of the hydrogenation reactor was taken for composition testing, and the conversion of aldehyde, acid, ester and selectivity to butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
[ example 13 ]
The butanol plant waste stream was recycled as in example 2, except that the hydrogenation catalyst in step (3) was the catalyst F prepared in the preceding preparatory example.
A sample at the outlet of the hydrogenation reactor was taken for composition testing, and the conversion of aldehyde, acid, ester and selectivity to butanol were calculated, with the results shown in table 1. In addition, the process system shown in fig. 1 was tested for long-term stability, and the results are shown in table 1, where the selectivity of butanol was taken as the reference and the system operation period was measured when the selectivity of butanol decreased to 80%.
TABLE 1 test results
Comparative example 1
Reference example 2 the method of treating butanol plant waste stream differs only in that: the pretreatment of the waste liquid in step 1, i.e., the removal of metal ions from the waste liquid by ion exchange resin, was not performed, and the other treatment methods were the same as those in example 2. The results of the performance tests are shown in table 1.
Comparative example 2
Reference example 2 the method of treating butanol plant waste stream differs only in that: the feeding buffer tank in the step 2 is replaced by a feeding buffer tank without a metal wire wound filter at the bottom, and other processing methods are consistent with the example 2. The results of the performance tests are shown in table 1.
Comparative example 3
Reference example 2 the method of treating butanol plant waste stream differs only in that: the supported catalyst was prepared according to the method of patent CN112321386A example 1, and applied to the hydrogenation reactor (replacing hydrogenation catalyst E) in example 2 of the present invention for catalytic hydrogenation, and the other treatment methods were the same as those in example 2. The results of the performance tests are shown in table 1.
Comparative example 4
The butanol plant waste stream was treated according to the method of example 2, differing only in the following two points: 1) the pretreatment operation of the waste liquid in the step 1 is not carried out; 2) the supported catalyst was prepared according to the method of patent CN112321386A example 1 and applied to the hydrogenation reactor (replacing hydrogenation catalyst E) in example 2 of the present invention for catalytic hydrogenation. The other treatment methods were the same as in example 2. The results of the performance tests are shown in table 1.
As can be seen from the test results of example 2 and comparative example 1 in table 1, the pretreatment of the butanol plant waste liquid by the strongly acidic ion exchange resin before the hydrogenation reaction, controlling the metal ion content below 1ppm, can significantly improve the stable operation and cycle of the system. The test results of comparative examples 1 to 8 and examples 11 to 13 show that the increase of the Cu content in the hydrogenation catalyst is beneficial to improving the conversion rate of aldehyde, acid and ester, and the increase of the Zn content is beneficial to improving the selectivity of butanol, but the long-term stable operation of the device is influenced to a certain extent when the Cu and Zn contents are too high. As can be seen from the test results of example 2 and comparative example 2, the removal of the remaining solid particles by the wire wound filter before the hydrogenation reaction also improves the stable operation period of the apparatus to some extent. Comparative examples 3 to 4 the catalyst was replaced with a hydrogenation catalyst composed of other metals, and the stable operation period of the apparatus was significantly shortened, especially without resin pretreatment, and at the same time, the conversion rates of aldehyde, acid, ester and butanol were significantly reduced, indicating that the method of the present invention has superior technical effects compared to the prior art.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for recycling waste liquid of a butanol device is characterized by comprising the following steps:
a. pretreating butanol device waste liquid through ion exchange resin filled in a fixed bed so as to control metal ions in the waste liquid to be below 1 ppm;
b. pressurizing the pretreated waste liquid by a booster pump, preferably 3-8MPa of the outlet pressure of the booster pump, fully mixing the waste liquid with high-pressure hydrogen in a static mixer, feeding the mixture into a fixed bed reactor for hydrogenation reaction, and hydrogenating aldehyde, acid and ester substances in the waste liquid to convert the aldehyde, acid and ester substances into alcohol; a hydrogenation catalyst is filled in the fixed bed reactor;
c. after the reaction is finished, removing hydrogen and other light components dissolved in the reaction liquid through a high-pressure degassing tank;
d. sending the degassed reaction liquid to a product refining tower, and rectifying and separating to obtain butanol;
preferably, the butanol plant waste stream comprises the following content ranges of components: 10-15% of butyraldehyde, 1-2% of butyric acid, 5-10% of butanol, 50-60% of esters, and 20-30% of carbon twelve and above substances.
2. The method for recycling waste liquid from a butanol production apparatus according to claim 1, wherein the ion exchange resin is an ion exchange resin having a sulfonic acid functional group, preferably one or more of LX-160, LX-36 and LSC-485.
3. The method for recycling waste liquid of a butanol device according to claim 2, wherein the operating pressure in step a is 45 to 50kpa gauge pressure, the operating temperature is 30 to 90 ℃, preferably 40 to 50 ℃, and the space velocity is 1 to 1.5h-1。
4. The method for recycling waste liquid from a butanol plant according to any one of claims 1 to 3, wherein the hydrogenation catalyst is a catalyst containing one or more metals selected from the group consisting of copper, aluminum, zinc, cobalt, and nickel; preferably, the hydrogenation catalyst is a mixture containing metal copper, aluminum and zinc in a molar ratio of (0.8-1.3) to 1 (0.1-0.3).
5. The method for recycling waste liquid of a butanol device as claimed in claim 4, wherein the hydrogenation reaction conditions in step b are that the operation pressure is 4-6MPa gauge pressure and the operation temperature is 160-220 ℃, preferably 180-200 ℃.
6. The method for recycling waste liquid of a butanol device according to claim 5, wherein the space velocity of the raw material for the hydrogenation reaction in step b is 0.5 to 3 hours-1Preferably 1-2h-1。
7. The method for recycling the waste liquid of the butanol device according to claim 1, wherein a feed buffer tank is arranged at the feed end of the static mixer in the step b, and a metal wire wound filter is arranged at the discharge port at the bottom of the feed buffer tank so as to remove solid particles carried in the waste liquid before the waste liquid enters the fixed bed reactor and avoid poisoning a hydrogenation catalyst;
preferably, the feed buffer tank is operated at a pressure of 40 to 50KPa gauge and at a temperature of 35 to 40 ℃.
8. The method of recycling butanol plant waste liquid according to claim 1, wherein the top of the high pressure degassing tank is provided with a demister to reduce liquid phase entrainment in the gas phase;
preferably, the operating conditions of the high-pressure degassing tank are an operating pressure gauge pressure of 90-100kpa and an operating temperature of 40-50 ℃.
9. The method for recycling the waste liquid of the butanol device according to claim 1, wherein butanol is produced from the side line of the product refining tower in the step d, the non-condensable gas discharged from the top of the tower is returned to the butanol device for recycling, and heavy components are removed from the bottom of the tower.
10. The method for recycling waste liquid of a butanol device according to claim 9, wherein the rectification separation conditions in step d are as follows: the operation pressure gauge pressure at the top of the tower is 10-15kpa, the operation temperature is 110-; the operating pressure gauge pressure of the tower kettle is 35-40kpa, and the operating temperature is 135-; the side line operating temperature is 123-.
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| CN101973846A (en) * | 2010-11-03 | 2011-02-16 | 淄博诺奥化工有限公司 | Method for producing mixed butanol and coarse octanol by using waste liquid discharged from octanol device as raw material |
| 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 |
| CN112321386A (en) * | 2020-11-04 | 2021-02-05 | 吉林市道特化工科技有限责任公司 | Method for hydrotreating butanol and octanol residual liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101973846A (en) * | 2010-11-03 | 2011-02-16 | 淄博诺奥化工有限公司 | Method for producing mixed butanol and coarse octanol by using waste liquid discharged from octanol device as raw material |
| 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 |
| CN112321386A (en) * | 2020-11-04 | 2021-02-05 | 吉林市道特化工科技有限责任公司 | Method for hydrotreating butanol and octanol residual liquid |
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| CN114534287A (en) * | 2022-02-13 | 2022-05-27 | 河北首朗新能源科技有限公司 | Distillation degassing device and degassing method |
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