CN103553876A - Liquid phase hydrogenation method for residual liquids of butanol and octanol - Google Patents
Liquid phase hydrogenation method for residual liquids of butanol and octanol Download PDFInfo
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- CN103553876A CN103553876A CN201310503293.0A CN201310503293A CN103553876A CN 103553876 A CN103553876 A CN 103553876A CN 201310503293 A CN201310503293 A CN 201310503293A CN 103553876 A CN103553876 A CN 103553876A
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- 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
- C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
Abstract
The invention discloses a liquid phase hydrogenation method for residual liquids of butanol and octanol. The liquid phase hydrogenation method is characterized by comprising the steps of firstly, carrying out fixed bed liquid catalytic hydrogenation reaction on the residual liquids of butanol and octanol, and then, rectifying and separating to obtain butanol and octanol, wherein a rectifying unit comprises a dehydrating tower, a butanol tower and an octanol tower. A catalyst for the hydrogenation reaction is composed of a carrier and active components, wherein the carrier is one of silicon dioxide and silica sol, the active components include Ni and Zn, Ni accounts for 10-50wt% of the total mass of the catalyst, and Zn accounts for 5-30wt% of the total mass of the catalyst; the catalyst is prepared by using a co-precipitation method. The catalyst used in the method is simple in component and preparation, the residual liquids of butanol and octanol are simple in treatment process and high in utilization ratio, and the purity of a product is high.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to the method for a kind of fourth octanol raffinate liquid-phase hydrogenatin.
Technical background
Butanols and octanol (being called for short fourth octanol) are mainly for the production of plasticizer phthalic acid dioctyl ester (DOP) and dibutyl phthalate (DBP).Along with the development of China's plastics industry, market is to the requirement of fourth octanol in cumulative year after year, and the production capacity of domestic butyl octanol unit is also increasing year by year.The vaporizer of butyl octanol unit reactor, phase splitter and weight-removing column etc. all have a small amount of ejecta, the mixed solution of discharging is called fourth octanol raffinate, is equivalent to 10% left and right of fourth octanol quality product, and wherein contains a large amount of valuable compositions, but complicated owing to forming, the multiplex fuel of doing of past.The device of domestic existing recycling fourth octanol raffinate is as batch fractionating tower etc., and the technique of employing is unreasonable, reclaims the of poor quality of product, and yield is low, and economic benefit is undesirable.As CN101423455A, Wu Jinyuan etc. (butanol and octanol waste liquid recovery technology is improved. petrochemical complex, 1999,28:832～834), Wang Lei (recycling of butanols and octanol raffinate. petrochemical complex, 2006,35 (8): 782～784), Xing Meixia (the reclaiming clean technology of butanol and octanol waste liquid. Inner Mongol petrochemical complex, 2000,7:53～54) etc. all carried out the work of this respect, but be all directly from waste liquid, to fractionate out butyraldehyde, butanols, C8 solvent substantially, remaining raffinate is used as oil fuel again.
CN101973846A discloses a kind of method that waste liquid of take butyl octanol unit discharge is raw material production mixed butyl alcohol and thick octanol, the method is by raw material fractionation unit, hydrogenation synthesis unit and product rectification cell form, mixed butyl alcohol purity >=the 95wt% producing, the thick octanol purity >=97wt% of production.But this technique has increased raw material fractionation unit before reaction, flow process is comparatively complicated, and cost of investment is large.CN101892066A discloses the production technique that under a kind of alkaline liquid cracking agent, fourth octanol raffinate is cracked into carbon four and carbon eight.Carbon four, carbon eight that this technique is not produced through hydrotreatment are the mixture of aldehyde and alcohol, and utility value is low.CN101913991A discloses a kind of recovery method of butanol and octanol waste liquid through hydrocracking, by waste liquid being removed to the above cut of C16 and salinity, the cut below C16 is carried out to hydrogenation and cracking, then isolates effective cut of butanols, octanol, C5～C7.The method, owing to removing the above cut of C16, has reduced the utilization ratio of fourth octanol raffinate.。
Fourth octanol raffinate hydrogenation process is mainly that aldehyde, the unsaturated alcohol hydrogenation in raffinate generates corresponding alcohol, and the long carbochain component of part generation hydrogenation, is cracked into the alcohol of short carbon chain, and used catalyst belongs to aldehyde hydrogenating catalyst category.Aldehyde hydrogenation is divided into gas phase hydrogenation and liquid-phase hydrogenatin, and liquid-phase hydrogenatin, because energy consumption is low, hydrogenation is effective, is widely adopted in recent years.CN1478596A discloses a kind of catalyzer of mixture liquid-phase hydrogenatin isooctyl alcohol processed of different octanal, and this catalyzer be take Ni as active ingredient, take alkaline-earth metal or/and aluminum oxide is promotor, and siliceous compound is carrier.After hydrogenation, different octanal has remnants, and hydrogenation rate is 96%.CN102309968A discloses a kind of aldehyde liquid phase hydrogenating catalyst, nickel or its oxide compound are 8～35%, at least one element in IAHuo IIA family or its oxide compound are (0.01～2.0) wt%, in IIIA or IV group, at least one element or its oxide compound are (0.01～20.0) wt%, rare earth element is (0.01～5) wt%, aluminum oxide is carrier, and this catalyst low-temperature activity is high, but catalyzer forms comparatively complexity.CN102059121A discloses a kind of lanthanum modified nickel-copper octanol hydrorefining catalyst, with γ-Al
2o
3for carrier, ambrose alloy is active ingredient, and lanthanum is auxiliary agent, and octenal, disloyalty aldehyde, octenol hydrogenation rate all reach more than 95%.CN1730151 discloses a kind of catalyzer of thick octanol liquid-phase hydrogenatin refining reaction.Catalyst activity component is Ni, and rare earth metal is promotor, and aluminum oxide is carrier, adds silicon and makees auxiliary agent.CN1275439A discloses a kind of liquid phase hydrogenating catalyst for unsaturated aldehyde liquid-phase hydrogenatin technique.This catalyzer is done carrier by silicon-dioxide, and nickel is the first active ingredient, and other active ingredient is cobalt, molybdenum, chromium, potassium.Active ingredient is complicated.
European patent EP 394842 discloses the liquid phase hydrogenating catalyst of BASF, and chief component is Ni-Cu, and only, when 180 ℃ of service temperatures, pressure 2.5～35MPa, this catalyzer just can make raw material 100% transform.JP61172838 discloses the patent that Mitsubishi changes into Co., Ltd., and used catalyst is Ni-Cr/ diatomite catalyzer, and service temperature is 80～145 ℃, and pressure is 5MPa.US Patent No. 6201160B discloses a kind of technique and catalyzer thereof by aldehyde shortening alcohol processed, and catalyzer is wherein that copper is impregnated into SiO
2on carrier, optionally contain the metals such as Mg, Ba, Zn, Cr.US Patent No. 4021497 discloses a kind of octenal Hydrogenation octanol Co series catalysts, and adds Ni, Cu and Mg as auxiliary agent, and with P
2o
5the tetra-sodium that form meter content is 0.5～15wt% or poly-phosphate at least one add catalyzer as carrier.Romania patent RO9452B1 and RO94237B1 disclose a kind of CuCr catalyzer of octenal Hydrogenation octanol, add the 3rd component Ni as catalyst adjuvant, and employing silicon is support of the catalyst.Russian patent RU2052445C1 discloses a kind of copper zinc mixed oxide as auxiliary agent and carrier, take gac as carrier, catalyzer consist of Cu(25.0～53.0) wt%, ZnO(22.0～36.0) wt%, CaO(6.0～12.0) wt%, Al
2o
3(16.0～32.0) wt%, graphite (1.4～2.9) wt%, MnO1.5wt%, birch gac (BAS) 2.0wt%+0.1wt%Cr
2o
3.
In above patent and bibliographical information, aspect fourth octanol raffinate treatment process, there is the problems such as residual liquid rate is low, complex treatment process.Aspect catalyzer, institute's invention catalyzer is mostly for aldehyde Hydrogenation alcohol, and raw material forms relatively simple, and the composition of catalyzer is also comparatively complicated.And be exclusively used in, form complicated fourth octanol raffinate hydrogenation catalyst report seldom, although disclose a kind of fourth octanol raffinate hydrogenation, cracking dual-function catalyst in CN101913991A, main ingredient is cupric oxide, zinc oxide, aluminum oxide, silicon-dioxide and nickel oxide, also adds the auxiliary agents such as Na, Ca, Ba simultaneously.But this catalyzer, for having removed the hydrogenation process of the fourth octanol raffinate of the above heavy constituent of C16, is not directly used in the hydrogenation process of the more complicated fourth octanol raffinate of composition.And the treatment process of the inventive method fourth octanol raffinate is simple, residual liquid rate is high, catalyzer forms and preparation method is simple.
Summary of the invention
The object of the present invention is to provide the method for a kind of fourth octanol raffinate liquid-phase hydrogenatin.Relate in particular to the method for making of a kind of fourth octanol raffinate treatment process and a kind of fourth octanol raffinate liquid phase hydrogenating catalyst.To solve, fourth octanol residual liquid rate in prior art is low, the problem of complex treatment process, and the method adopts rectifying separation after the first liquid-phase hydrogenatin of fourth octanol raffinate to obtain the combination process of butanols and octanol, and raw material is without pre-treatment, and technique is simple; Hydrogenation unit adopts a kind of catalyzer that Ni, Zn be carrier as active ingredient, silicon oxide of take, and catalyzer forms simple, containing auxiliary agents such as Cu, Mg, La; Adopt a step coprecipitation method preparation, preparation technology is simple; Catalyzer has hydrogenation and cracking is difunctional, fourth octanol raffinate partly can be grown to the cracking of carbochain heavy constituent, is hydrogenated into short carbon chain alcohol, improves the utilization ratio of fourth octanol raffinate.Butanols, octanol yield, purity after the method is processed are high.
The present invention is the method for a kind of fourth octanol raffinate liquid-phase hydrogenatin, relates to a kind of method for making and treatment process of fourth octanol raffinate hydrogenation catalyst; It is characterized in that:
Described catalyzer is comprised of carrier and active ingredient, and carrier is a kind of in silicon-dioxide, silicon sol, and active ingredient is Ni and Zn, wherein Ni accounts for 10～50wt% of catalyzer total mass, preferred 20～40wt%, Zn accounts for 5～30wt% of catalyzer total mass, preferably 10～20wt%;
Described catalyzer adopts coprecipitation method to make, and comprises the following steps:
1. silicon-dioxide or silicon sol are added in the nitrate aqueous solution of nickel and zinc and stir;
2. precipitation agent is slowly added to above-mentioned solution, under certain condition co-precipitation;
3. by above-mentioned precipitation after filtration, compression molding after washing, dry, roasting;
4. the catalyst precursor after moulding is packed in fixed-bed reactor and uses hydrogen reducing under certain condition, obtain fourth octanol raffinate liquid phase hydrogenating catalyst Ni-Zn/SiO
2;
In described catalyst preparation process, precipitation agent used is K
2cO
3, Na
2cO
3, NH
4hCO
3, (NH
4)
2cO
3, a kind of in KOH, NaOH or ammoniacal liquor; Precipitation temperature is controlled at 40～60 ℃, and after precipitation, the pH value of mixing solutions is 6～8, ageing 1～3h after precipitation; Filter, wash to neutral, drying conditions is dry 8～12h at 80～120 ℃, and roasting condition is roasting 3～5h at 300～500 ℃; Reductive condition is, 350～550 ℃ of reduction temperatures, and pressure is 1～3MPa, and hydrogen, catalyst volume are than 200～1000:1, and the recovery time is 3～5h;
Described treatment process is divided into hydrogenation unit and rectifying separation unit, and fourth octanol raffinate first carries out the reaction of fixed bed liquid phase catalytic hydrogenation, and then reaction product obtains butanols and octanol through the separation of rectifying separation unit:
Described hydrogenation unit is fixed bed liquid-phase hydrogenatin reaction, after fourth octanol raffinate mixes with hydrogen, with liquid form, from top, enters hydrogenator; Under catalyst action, there is hydrogenation and scission reaction in fourth octanol raffinate; The operational condition of hydrogenator is, 130～200 ℃ of temperature of reaction, reaction pressure 1.5～3MPa, hydrogen liquor ratio 100～300:1, LHSV=0.3～1.5h
-1;
Described rectification cell is divided into three towers operations, and hydrogenation after product is introduced into dehydration tower dehydration, enters afterwards butanols tower, overhead extraction butanols, and materials at bottom of tower enters octanol tower, overhead extraction octanol, a small amount of heavy constituent is from extraction at the bottom of tower; The operational condition of three towers is respectively:
1. dehydration column overhead temperature is 80～100 ℃, 110～130 ℃ of column bottom temperatures; Tower top pressure is normal pressure;
2. butanols column overhead temperature is 60～75 ℃, 130～150 ℃ of column bottom temperatures, and tower top pressure is absolute pressure 10～15KPa;
3. octanol column overhead temperature is 110～130 ℃, 150～180 ℃ of column bottom temperatures, and tower top pressure is absolute pressure 10～15KPa;
Fourth, octanol total recovery > 85% after present method is processed, butanols and octanol purity >=97%.
Fourth octanol raffinate liquid phase hydrogenating method of the present invention compared with prior art tool has the following advantages:
1, raw material is without pre-treatment, and simplification of flowsheet, reduces investment.
2, fourth octanol raffinate hydrogenation catalyst has hydrogenation and cracking is difunctional, has improved the utilization ratio of fourth octanol raffinate, and catalyzer forms, preparation technology is simple.
Accompanying drawing explanation
The process flow diagram of the method that accompanying drawing 1 is the liquid-phase hydrogenatin of a kind of fourth octanol of the present invention raffinate: be respectively 1, hydrogenator; 2, cold high pressure separator; 3, dehydration tower, 4, butanols tower; 5, octanol tower.
By reference to the accompanying drawings fourth octanol raffinate treatment process is further elaborated.First fourth octanol raffinate and hydrogen enter fixed-bed reactor with liquid form after mixing, through liquid phase catalytic hydrogenation reaction after product, enter cold high pressure separator, isolating hydrogen can be recycled, liquid enters dehydration tower dehydration, and tower top material enters Waste Water Treatment after cooling, and at the bottom of tower, liquid enters butanols tower, overhead extraction butanols, materials at bottom of tower enters octanol tower, overhead extraction octanol, and at the bottom of tower, heavy constituent can be used as oil fuel.Concrete operations parameter is shown in embodiment.
Embodiment
98.5g nickelous nitrate and 91.3g zinc nitrate are dissolved in 2L deionized water, by 60gSiO
2powder adds above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the aqueous sodium carbonate of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 40 ℃ of precipitation temperatures, after stirring ageing 1h, filter and wash to neutrality, dry 8h at 120 ℃, at 500 ℃, roasting 3h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 1.0MPa, 500 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 2h, obtain catalyst sample 1 under than 200:1 condition.
Fourth octanol raffinate and hydrogen enter hydrogenator with liquid form from top after mixing, and catalyzer of the present invention is housed in reactor.The operational condition of hydrogenator is, 130 ℃ of temperature of reaction, reaction pressure 3.0MPa, hydrogen liquor ratio 300:1, LHSV=0.3h
-1.Hydrogenation after product is separated with product liquid by hydrogen through cold high pressure separator, hydrogen recycle utilization, and product liquid enters dehydration tower and removes water and a small amount of light constituent.Dehydration tower operational condition is, 80 ℃ of tower top temperatures, and 110 ℃ of column bottom temperatures, tower top pressure is normal pressure.After dehydration, material enters butanols tower, and from overhead extraction butanols, butanols tower operational condition is, 60 ℃ of tower top temperatures, and 130 ℃ of column bottom temperatures, tower top pressure is 10KPa(absolute pressure).Butanols materials at bottom of tower enters octanol tower, from overhead extraction octanol, is remaining heavy constituent at the bottom of tower, and octanol tower operational condition is: 110 ℃ of tower top temperatures, and 150 ℃ of column bottom temperatures, tower top pressure is 10KPa(absolute pressure).
147.8g nickelous nitrate and 68.5g zinc nitrate are dissolved in 2L deionized water, by 55gSiO
2powder adds above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the wet chemical of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 8, control approximately 50 ℃ of precipitation temperatures, after stirring ageing 2h, filter and wash to neutrality, dry 10h at 110 ℃, at 450 ℃, roasting 4h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 2.0MPa, 450 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 3h, obtain catalyst sample 2 under than 300:1 condition.
197g nickelous nitrate and 45.7g zinc nitrate are dissolved in 2L deionized water, by 50gSiO
2powder adds above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the ammonium bicarbonate aqueous solution of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 60 ℃ of precipitation temperatures, after stirring ageing 3h, filter and wash to neutrality, dry 12h at 100 ℃, at 400 ℃, roasting 5h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 3.0MPa, 400 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 4h, obtain catalyst sample 3 under than 400:1 condition.
Embodiment 4
147.8g nickelous nitrate and 91.3g zinc nitrate are dissolved in 2L deionized water, by 50gSiO
2powder adds above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the ammonium carbonate solution of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 50 ℃ of precipitation temperatures, after stirring ageing 2h, filter and wash to neutrality, dry 12h at 120 ℃, at 350 ℃, roasting 5h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 2.0MPa, 350 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 4h, obtain catalyst sample 4 under than 500:1 condition.
98.5g nickelous nitrate and 68.5g zinc nitrate are dissolved in 2L deionized water, by 65gSiO
2powder adds above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the aqueous sodium hydroxide solution of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 50 ℃ of precipitation temperatures, after stirring ageing 2h, filter and wash to neutrality, dry 8h at 120 ℃, at 450 ℃, roasting 4h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 2.0MPa, 500 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 2h, obtain catalyst sample 5 under than 600:1 condition.
Embodiment 6
197g nickelous nitrate and 68.5g zinc nitrate are dissolved in 2L deionized water, by 45gSiO
2powder adds above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the potassium hydroxide aqueous solution of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 50 ℃ of precipitation temperatures, after stirring ageing 2h, filter and wash to neutrality, dry 8h at 120 ℃, at 450 ℃, roasting 4h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 2.0MPa, 500 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 2h, obtain catalyst sample 6 under than 700:1 condition.
Embodiment 7
147.8g nickelous nitrate and 68.5g zinc nitrate are dissolved in 2L deionized water, 183.3g silicon sol is added to above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation 10% ammonia soln afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 50 ℃ of precipitation temperatures, after stirring ageing 2h, filter and wash to neutrality, dry 8h at 120 ℃, at 450 ℃, roasting 4h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 2.0MPa, 500 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 2h, obtain catalyst sample 7 under than 700:1 condition.
Embodiment 8
147.8g nickelous nitrate and 68.5g zinc nitrate are dissolved in 2L deionized water, 183.3g silicon sol is added to above-mentioned solution stirring 15 minutes, add above-mentioned solution to carry out co-precipitation the aqueous sodium carbonate of 1.2mol/L afterwards, after precipitation, the pH value of mixed solution is 7, control approximately 50 ℃ of precipitation temperatures, after stirring ageing 2h, filter and wash to neutrality, dry 8h at 120 ℃, at 450 ℃, roasting 4h, then obtains catalyst precursor through compression molding.Pack catalyst precursor into 20mL fixed-bed reactor, at pressure 2.0MPa, 500 ℃ of temperature, hydrogen and catalyst volume, with hydrogen reducing 2h, obtain catalyst sample 8 under than 800:1 condition.
The fourth octanol raffinate processing technological flow of embodiment 2～8 is with embodiment 1.Embodiment 1～8 fourth octanol used raffinate table composed as follows.
Table 1 fourth octanol raffinate forms
| Title | C4 aldehyde | C4 alcohol | C5～C7 | C8 aldehyde | C8 alcohol | C9+ | Water |
| Form % | 3.5 | 15.5 | 1.6 | 10.2 | 32 | 34.7 | 2.5 |
Catalyzer composition and the specific surface area of embodiment 1～8 are as shown in table 2.
The composition of table 2 catalyzer and specific surface area
| Project | Ni content/% | Zn content/% | SiO 2Content/% | Specific |
| Embodiment | ||||
| 1 | 19.9 | 19.7% | 60.4 | 252 |
| |
30.2 | 14.7 | 55.1 | 240 |
| |
38.6 | 10.5 | 50.9 | 238 |
| Embodiment 4 | 29.8 | 19.8 | 50.4 | 235 |
| |
19.8 | 15.1 | 65.1 | 251 |
| Embodiment 6 | 38.7 | 15.2 | 46.1 | 233 |
| Embodiment 7 | 29.6 | 14.8 | 55.6 | 201 |
| Embodiment 8 | 19.7 | 19.8 | 60.5 | 210 |
The fourth octanol raffinate treatment process condition of embodiment 1～8 is as table 3, shown in table 4.
Table 3 embodiment 1～8 hydrogenation unit operational condition
| Project | Temperature of reaction/℃ | Reaction pressure/MPa | Hydrogen liquor ratio/v:v | LHSV,h -1 |
| Embodiment 1 | 130 | 3 | 300 | 0.3 |
| |
150 | 2.5 | 200 | 0.5 |
| |
170 | 2.0 | 100 | 0.5 |
| Embodiment 4 | 200 | 1.5 | 200 | 1.0 |
| |
200 | 3 | 100 | 1.5 |
| Embodiment 6 | 150 | 2.0 | 200 | 0.5 |
| Embodiment 7 | 150 | 2.0 | 200 | 0.5 |
| Embodiment 8 | 150 | 2.0 | 200 | 0.5 |
Table 4 embodiment 1～8 rectification cell operational condition
After embodiment 1～8 hydrogenation, yield, the purity of butanols and octanol are as shown in table 5.
Table 5 butanols and octanol yield, purity
| Project | Butanols yield, % | Butanols purity, % | Octanol yield, % | Octanol purity, |
| Embodiment | ||||
| 1 | 29.2 | 98.2 | 56.5 | 98.5 |
| |
28.7 | 98.7 | 57.0 | 98.2 |
| |
28.2 | 98.9 | 55.9 | 98.3 |
| Embodiment 4 | 27.8 | 97.9 | 58.0 | 97.5 |
| |
27.9 | 98.1 | 55.6 | 98.0 |
| Embodiment 6 | 28.5 | 98.5 | 57.2 | 97.8 |
| Embodiment 7 | 30.0 | 97.2 | 55.4 | 97.6 |
| Embodiment 8 | 29.5 | 98.1 | 55.7 | 98.8 |
Claims (1)
1. a method for fourth octanol raffinate liquid-phase hydrogenatin, relates to method for making and the treatment process of fourth octanol raffinate hydrogenation catalyst; It is characterized in that:
Described catalyzer is comprised of carrier and active ingredient, and carrier is a kind of in silicon-dioxide, silicon sol, and active ingredient is Ni and Zn, and wherein Ni accounts for 10～50wt% of catalyzer total mass, and Zn accounts for 5～30wt% of catalyzer total mass;
Described catalyzer adopts coprecipitation method to make, and comprises the following steps:
1. silicon-dioxide or silicon sol are added in the nitrate aqueous solution of nickel and zinc and stir;
2. precipitation agent is slowly added to above-mentioned solution, under certain condition co-precipitation;
3. by above-mentioned precipitation after filtration, compression molding after washing, dry, roasting;
4. the catalyst precursor after moulding is packed in fixed-bed reactor and uses hydrogen reducing under certain condition, obtain fourth octanol raffinate liquid phase hydrogenating catalyst Ni-Zn/SiO
2;
In described catalyst preparation process, precipitation agent used is K
2cO
3, Na
2cO
3, NH
4hCO
3, (NH
4)
2cO
3, a kind of in KOH, NaOH or ammoniacal liquor; Precipitation temperature is controlled at 40～60 ℃, and after precipitation, the pH value of mixing solutions is 6～8, ageing 1～3h after precipitation; Filter, wash to neutral, drying conditions is dry 8～12h at 80～120 ℃, and roasting condition is roasting 3～5h at 300～500 ℃; Reductive condition is, 350～550 ℃ of reduction temperatures, and pressure is 1～3MPa, and hydrogen, catalyst volume are than 200～1000:1, and the recovery time is 3～5h;
Described treatment process is divided into hydrogenation unit and rectifying separation unit, and fourth octanol raffinate first carries out the reaction of fixed bed liquid phase catalytic hydrogenation, and then reaction product obtains butanols and octanol through the separation of rectifying separation unit:
Described hydrogenation unit is fixed bed liquid-phase hydrogenatin reaction, after fourth octanol raffinate mixes with hydrogen, with liquid form, from top, enters hydrogenator; Under catalyst action, there is hydrogenation and scission reaction in fourth octanol raffinate; The operational condition of hydrogenator is, 130～200 ℃ of temperature of reaction, reaction pressure 1.5～3MPa, hydrogen liquor ratio 100～300:1, LHSV=0.3～1.5h
-1;
Described rectification cell is divided into three towers operations, and hydrogenation after product is introduced into dehydration tower dehydration, enters afterwards butanols tower, overhead extraction butanols, and materials at bottom of tower enters octanol tower, overhead extraction octanol, a small amount of heavy constituent is from extraction at the bottom of tower; The operational condition of three towers is respectively:
1. dehydration column overhead temperature is 80～100 ℃, 110～130 ℃ of column bottom temperatures; Tower top pressure is normal pressure;
2. butanols column overhead temperature is 60～75 ℃, 130～150 ℃ of column bottom temperatures, and tower top pressure is absolute pressure 10～15KPa;
3. octanol column overhead temperature is 110～130 ℃, 150～180 ℃ of column bottom temperatures, and tower top pressure is absolute pressure 10～15KPa;
Fourth, octanol total recovery > 85% after present method is processed, butanols and octanol purity >=97%.2, in accordance with the method for claim 1, it is characterized in that:
Described catalyzer is comprised of carrier and active ingredient, and carrier is a kind of in silicon-dioxide, silicon sol, and active ingredient is Ni and Zn, and wherein Ni accounts for 20～40wt% of catalyzer total mass, and Zn accounts for 10～20wt% of catalyzer total mass.
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|---|---|---|---|
| CN201310503293.0A CN103553876B (en) | 2013-10-23 | 2013-10-23 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
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|---|---|---|---|
| CN201310503293.0A CN103553876B (en) | 2013-10-23 | 2013-10-23 | Liquid phase hydrogenation method for residual liquids of butanol and octanol |
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| 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 |
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| 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 |
| 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 |
| 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 |
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| CN111215072B (en) * | 2018-11-23 | 2023-06-09 | 中国石油化工股份有限公司 | Nickel-silicon composite oxide, preparation method thereof, catalyst containing nickel-silicon composite oxide and application of nickel-silicon composite oxide |
| CN109876812A (en) * | 2019-01-25 | 2019-06-14 | 武汉聚川科技有限公司 | A kind of preparation method of nickel-base hydrogenation catalyst |
| 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 |
| 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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| CN112321386B (en) * | 2020-11-04 | 2023-05-09 | 吉林市道特化工科技有限责任公司 | Method for hydrotreating butanol-octanol raffinate |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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