CN1217899C - Isooctanol refining process and its catalyst - Google Patents

Isooctanol refining process and its catalyst Download PDF

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CN1217899C
CN1217899C CN 02151550 CN02151550A CN1217899C CN 1217899 C CN1217899 C CN 1217899C CN 02151550 CN02151550 CN 02151550 CN 02151550 A CN02151550 A CN 02151550A CN 1217899 C CN1217899 C CN 1217899C
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catalyst
catalyzer
phase
isooctanol
ethyl
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CN1511816A (en
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程玉春
杨霞
郝树仁
尹长学
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Qilu Petrochemical Co of Sinopec
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Abstract

The present invention relates to an isooctanol refining process and a catalyst thereof, particularly to a process for carrying out liquid phase hydrogenation for coarse isooctanol containing the unsaturates of isooctyl aldehyde, oetenol, etc. to refine isooctanol and a catalyst thereof. The active component of the catalyst is nickel, a carrier is alumina and the catalyst selectivity contains an alkaline earth metal as an accelerating agent. The catalyst is prepared by an immersion method, wherein the phases of the carrier alumina are theta-Al2O3 phases and gamma-Al2O3 phases, and can also selectivity contain a small quantity of alpha-Al2O3 phases. The liquid phase hydrogenation process of the present invention and the catalyst are used for carrying out coarse isooctanol refining reaction. The capacity of the catalyst for adapting to a process condition is strong, the hydrogenation activity is high, the isooctanol yield is larger than 100% and the purity and the chrominance of the isooctanol are greatly improved.

Description

A kind of isooctyl alcohol process for refining and catalyzer thereof
Technical field
The present invention relates to a kind of isooctyl alcohol process for refining and catalyzer thereof, specifically, the present invention relates to a kind of purified technology and employed catalyzer thereof be carried out in thick isooctyl alcohol (wherein containing unsaturatess such as different octanal, octenol, octenal) liquid-phase hydrogenatin.
Background technology
Isooctyl alcohol (2-ethyl-1-hexanol, the industrial octanol that is commonly called as) production is a raw material with synthetic gas and propylene generally, and oxo process generates and mixes butyraldehyde under the effect of rhodium phosphine catalyst.
Main reaction:
Side reaction generates isobutyric aldehyde and propane.
Butyraldehyde-n condensation dehydration under the effect of catalyzer generates octenal (2-ethyl-2-alkene-1-hexanal):
Figure C0215155000031
2-ethyl hexenal (octenal)
The octenal hydrogenation generates isooctyl alcohol then:
2-ethyl hexenal (octenal) 2-Ethylhexyl Alcohol (isooctyl alcohol)
Octenal generate and hydrogenation process in except generation primary product isooctyl alcohol, also have a small amount of different octanal (2-ethyl-1-hexanal), octenol (2-ethyl-2-alkene-1 hexanol, also claim isooctene alcohol) etc. the generation of material, the existence of these materials will influence the purity and the colourity of isooctyl alcohol, needs further hydrofining that different octanal, octenol and residual octenal hydrogenation are generated isooctyl alcohol.By this finishing hydrogen means, reach the purpose that improves the isooctyl alcohol yield and improve the quality of products.
Octenal mixing raw material hydrogenation has two kinds of gas phase and liquid phases, characteristics such as liquid-phase hydrogenatin is low with energy consumption, product purity height and be better than gas phase hydrogenation.Gas phase hydrogenation generally adopts copper-based catalysts, for example: CuO-ZnO, CuO-ZnO-Al 2O 3Deng catalyzer.The catalyzer that liquid-phase hydrogenatin generally adopts nickel system, precious metal system, nickel-copper system or copper and other metal to form, for example: loading type Ni-Cr catalyzer, Ni-Al 2O 3-ZrO 2Catalyzer, Ni-ZrO 2-CuO-MnO catalyzer, Ni-Cr-Mo-K/SiO 2Catalyzer, Ni-Al 2O 3-TiO 2Catalyzer, Ni-Cu-Cr-base metal catalysts or the like.U.S. Pat 6201160B1 discloses a kind of technology and catalyzer thereof by aldehyde shortening system alcohol, and catalyzer wherein is that the compound with copper is impregnated into SiO 2On the carrier, then by roasting preparation, this catalyzer can also optionally contain metals such as Mg, Ba, Zn, Cr.
After the main reaction of octenal hydrogenation, need to contain the further hydrogenation of mixture of a small amount of different octanal, octenol, octenal, obtain purified isooctyl alcohol, this unifining process requires catalyst activity higher, and performance is more excellent.Adopt the liquid-phase hydrogenatin method to carry out for this reason.
The catalyzer that is used for comprising mixture (mixture also comprises other materials such as the octenal sometimes) liquid-phase hydrogenatin (being the isooctyl alcohol refining reaction) of different octanal, octenol does not also have bibliographical information.And catalyzer of the present invention can reach this purpose.
Summary of the invention
Purpose of the present invention just provides a kind of technology and catalyzer thereof that materials such as different octanal, octenol, octenal are carried out liquid-phase hydrogenatin, promptly provides a kind of thick isooctyl alcohol is carried out purified technology and catalyzer thereof.
The characteristics of isooctyl alcohol process for refining of the present invention are to have used a kind of liquid phase hydrogenating catalyst, and described catalyzer is nickel-Al 2O 3System, nickel are active ingredient, Al 2O 3Carrier and auxiliary agent for catalyzer; Described catalyzer also can be nickel-alkaline-earth metal-Al 2O 3System, nickel are active ingredient, and alkaline-earth metal is the auxiliary agent of catalyzer, Al 2O 3Be carrier.
Above-mentioned catalyzer is with Al 2O 3Be carrier, preferably this Al 2O 3The thing of carrier is mainly θ-Al mutually 2O 3Phase and γ-Al 2O 3Phase can also optionally contain a spot of α-Al 2O 3Phase.This carrier has abundant macropore, good pore structure and pore distribution and distributes and physical strength for catalyzer provides higher specific surface area, good pore structure, and it is the Al of 38-56% that the present invention preferably adopts the weight water-intake rate 2O 3Carrier.
Catalyzer of the present invention is in catalyst weight, and nickel content (in nickel oxide) is 5-35wt.%, is preferably 10-20wt.%; Alkaline earth metal content (in the oxide compound of alkaline-earth metal) is 0-15wt.%, is preferably 0-5wt.%; Al 2O 3Content is 60-95wt.%, is preferably 75-90wt.%.
Al in the catalyzer of the present invention 2O 3Carrier with aluminum oxide powder, aluminium glue, pseudo-boehmite or active aluminum and water, pore-forming material, binding agent mediate, moulding, drying and roasting make.The kind of pore-forming material and binding agent and consumption are well known to a person skilled in the art, for example can comprise cellulose acetate, kapok, graphite, sesbania powder, Walocel MT 20.000PV, citric acid, nitric acid and its esters.During moulding, preparing carriers can be become diameter is that Φ 2-3mm, length are the strip of 3-12mm, or is prepared into the Raschig ring shape of internal diameter Φ 1-2mm, external diameter Φ 3-5mm, length 3-8mm.Drying temperature is generally 100-120 ℃, and maturing temperature is generally 750-1150 ℃.So just can obtain having high-ratio surface, hole prosperity, main thing is θ-Al mutually 2O 3Phase and γ-Al 2O 3Phase can also optionally contain a spot of α-Al 2O 3The carrier of phase.
Active constituent and promotor are impregnated on the above-mentioned carrier, just make catalyzer of the present invention through 450-850 ℃ of roasting again.In the catalyzer of the present invention, active component nickel adopts the method for soluble salt dipping to add in the catalyzer.When having base earth metal promoter, alkaline-earth metal is preferably magnesium and/or calcium, and they both can be dipped on the support of the catalyst altogether with soluble salt form and active constituent, and also the method that can adopt independent branch to soak is impregnated on the support of the catalyst.Dipping method is an ordinary method, can single-steeping, also can repeatedly flood.
The catalyzer of making according to method of the present invention has pore structure and reasonably pore distribution preferably, and has higher specific surface area, and the specific surface area of catalyzer is at 110m 2More than/the g, preferably at 125m 2More than/the g.
Catalyzer of the present invention, physical strength is good, and diameter is that the crushing strength of the catalyzer of Φ 2 can reach more than the 65N/cm, and diameter is that the crushing strength of the catalyzer of Φ 3 can reach more than the 70N/cm, and the side pressure strength of Raschig ring shape catalyzer all can reach more than the 60N/cm.
Above-mentioned catalyzer in use, nickel is reduced into the metallic nickel microcrystalline form, to improve activity of such catalysts.
The temperature of the thick isooctyl alcohol mixture of the present invention refining reaction (being different octanal mixture liquid-phase hydrogenatin reaction) is 80 ℃-260 ℃, and pressure is normal pressure-6.0MPa.
Utilize liquid-phase hydrogenatin technology of the present invention and catalyzer thereof to carry out thick isooctyl alcohol refining reaction, the ability that catalyzer adapts to processing condition is strong, and hydrogenation activity height, isooctyl alcohol yield have improved the purity and the colourity of isooctyl alcohol greatly greater than 100%.
Description of drawings
Figure of description is the reaction unit synoptic diagram of hydrogenatioin to produce iso octanol using iso octaldehyde mixture, among the figure: 1-liquid phase feed volume pump; The 2-mixing tank of vaporizing; The 3-tubular reactor; The 4-condenser; The 5-separator; The 6-potentiostat; The 7-wet flow indicator.
Further specify the present invention below in conjunction with embodiment.
Embodiment
Embodiment 1
Take by weighing the 500g aluminum oxide powder, add the sesbania powder of 1.8g and the Walocel MT 20.000PV of 3.4g, fully mediate, be shaped to the Raschig ring of internal diameter Φ 1.8mm, external diameter Φ 4.4mm, length 5.0mm, under 860 ℃ of temperature condition, handle, make alumina supporter; The nickelous nitrate dipping solution of preparation 1.3M (mol/l); Soak 120min; Decompose at 450 ℃ roasting temperatures, make catalyst A-1.Main technologic parameters in the catalyst A-1 in each components contents, the preparation process, pore structure data and intensity data see Table-1.
Change corresponding main technologic parameters in the concentration of steeping fluid in the above-mentioned preparation process and the preparation process, make catalyst A-2, A-3, A-4, A-5, A-6 respectively, wherein A-4, A-5, A-6 are twice dipping of steeping fluid, and for the first time identical with secondary impregnation concentration, dipping time, maturing temperature.Main technologic parameters, pore structure data and intensity data in A-2, A-3, A-4, A-5, each components contents of A-6, the preparation process are also listed in table-1, and the thing of catalyzer is mutually in X-ray diffraction sign table-1: main thing is θ-Al mutually 2O 3Phase and γ-Al 2O 3Phase also contains a spot of α-Al 2O 3Phase.
Table-1
Numbering The main technique condition Each components contents, wt.% Specific surface area m 2/g Side pressure strength N/cm
Impregnation concentration mol/l Dipping time min Maturing temperature ℃ NiO Al 2O 3
A-1 1.3 120 450 5 95 153.08 65.10
A-2 2.5 100 450 10 90 149.17 64.38
A-3 3.4 110 500 15 85 135.62 68.24
A-4 2.45 95 550 20 80 150.40 70.03
A-5 2.9 105 600 25 75 130.28 63.55
A-6 3.3 110 700 35 65 132.74 67.60
Embodiment 2
Weighing 500 gram aluminum oxide powders add 5.4 gram citric acids and 8.2 gram sesbania powder, mediate, and are shaped to the Raschig ring of internal diameter Φ 2.0mm, external diameter Φ 4.5mm, length 4.8mm, handle under 860 ℃ of temperature condition, make alumina supporter; The mixing salt dipping solution of compound concentration 2.30M (mol/l) nickelous nitrate, 0.75M (mol/l) magnesium nitrate; Dipping 110min; Under 450 ℃ temperature, roasting is decomposed, and makes catalyst B-1.Main technologic parameters in the catalyst B-1 in each components contents, the preparation process and pore structure data see Table-2.
Change corresponding main technologic parameters in the concentration of steeping fluid in the above-mentioned preparation process and the preparation process, make catalyst B-2, B-3, B-4, B-5 respectively.Main technologic parameters among catalyst B-2, B-3, B-4, the B-5 in each components contents, the preparation process and pore structure data are also listed in table-2, and the thing of catalyzer is mutually in X-ray diffraction sign table-2: main thing is θ-Al mutually 2O 3Phase and γ-Al 2O 3Phase also contains a spot of α-Al 2O 3Phase.
Table-2
Numbering The main technique condition Each components contents, wt.% Specific surface area m 2/g Side pressure strength N/cm
Mixing salt impregnation concentration mol/l Maturing temperature ℃ NiO MgO Al 2O 3
Nickelous nitrate Magnesium nitrate
B-1 2.30 0.75 500 10 2 88 153.07 68.15
B-2 3.50 1.40 550 15 4 81 130.60 65.43
B-3 3.80 4.00 600 20 12 68 135.45 68.08
B-4 3.80 2.60 650 20 8 72 130.67 71.50
B-5 3.85 1.40 500 20 4 76 128.08 65.00
Embodiment 3
Isooctyl alcohol mixture refining reaction device synoptic diagram is seen Figure of description.
It is the pipe of Φ 25mm that reaction tubes is selected internal diameter for use, the thermocouples tube of interpolation Φ 3mm.The catalyst loading granularity is the 10-20 order, and loading amount 65ml, reducing medium are hydrogen, and reduction temperature is 400 ℃-750 ℃, and reduction pressure is 0.5MPa.The operating liquid air speed is 5.0h -1, H 2/ liquid (mol/mol)=8: 1, running pressure 2.6MPa, 100 ℃, 110 ℃, 120 ℃ of temperature, each condition respectively turned round 4 hours.
The composition data of reacting raw materials used see Table-3.
Table-3
The constituent title Content (%)
Isopropylcarbinol 0.06
Propyl carbinol 1.20
Octane-iso 0.02
Isooctene 0.04
Different octanal 0.15
The 2-ethyl, the 4-methyl amyl alcohol 0.23
Isooctene alcohol 0.17
Isooctyl alcohol 97.60
The carbon lauryl alcohol 0.13
The different monooctyl ester of isocaprylic acid 0.15
Other 0.25
Use above-mentioned raw materials, under the effect of catalyst A-1, A-2, A-3, A-4, A-5, A-6, on reaction unit shown in the drawings, carry out liquid-phase hydrogenatin isooctyl alcohol refining reaction respectively, the results are shown in Table-4.
Use above-mentioned raw materials, under the effect of catalyst B-1, B-2, B-3, B-4, B-5, on reaction unit shown in the drawings, carry out liquid-phase hydrogenatin isooctyl alcohol refining reaction respectively, the results are shown in Table-5.
Table-4
Temperature ℃ Evaluate catalysts
A-1 A-2 A-3 A-4 A-5 A-6
100 Different octanal Content % 0.0129 0.0122 0.0106 0.0098 0.0108 0.0112
Hydrogenation rate % 91.40 91.87 92.93 93.47 92.80 92.53
Octenol Content % 0.0156 0.0133 0.0128 0.0113 0.0131 0.0128
Hydrogenation rate % 90.82 92.18 92.47 93.35 92.29 92.47
Isooctyl alcohol Content % 97.97 97.97 97.97 97.98 97.97 97.97
Yield % 100.4 100.4 100.4 100.4 100.4 100.4
110 Different octanal Content % 0.0116 0.0107 0.0099 0.0080 0.0099 0.0106
Hydrogenation rate % 92.27 93.71 94.18 95.29 94.18 93.76
Octenol Content % 0.0137 0.0117 0.0105 0.0096 0.0115 0.0120
Hydrogenation rate % 91.94 93.12 93.82 94.35 93.24 92.94
Isooctyl alcohol Content % 97.97 97.98 97.98 97.99 97.98 97.98
Yield % 100.4 100.4 100.4 100.4 100.4 100.4
120 Different octanal Content % 0.0110 0.0101 0.0090 0.0075 0.0091 0.0109
Hydrogenation rate % 92.67 93.27 94.00 95.00 93.93 92.73
Octenol Content % 0.0115 0.0106 0.0096 0.0069 0.0090 0.0111
Hydrogenation rate % 93.52 92.93 94.35 95.94 94.71 93.47
Isooctyl alcohol Content % 97.98 97.98 97.98 98.01 97.98 97.98
Yield % 100.4 100.4 100.4 100.4 100.4 100.4
Table-5
Temperature ℃ Evaluate catalysts
B-1 B-2 B-3 B-4 B-5
100 Different octanal Content % 0.0597 0.0402 0.0240 0.0294 0.0173
Hydrogenation rate % 60.20 73.20 84.00 80.40 88.47
Octenol Content % 0.1116 0.0837 0.0447 0.0357 0.0275
Hydrogenation rate % 34.35 50.76 73.71 79.00 83.82
Isooctyl alcohol Content % 97.63 97.76 97.89 98.09 98.03
Yield % 100.0 100.2 100.3 100.5 100.4
110 Different octanal Content % 0.0483 0.0364 0.0245 0.0214 0.0117
Hydrogenation rate % 67.80 75.73 83.67 85.73 92.20
Octenol Content % 0.0724 0.0594 0.0463 0.0316 0.0115
Hydrogenation rate % 57.41 65.06 72.76 81.41 93.24
Isooctyl alcohol Content % 97.74 97.79 97.87 98.02 97.97
Yield % 100.1 100.2 100.3 100.4 100.4
120 Different octanal Content % 0.0453 0.0305 0.0168 0.0156 0.0106
Hydrogenation rate % 69.80 79.67 88.80 89.60 92.93
Octenol Content % 0.0672 0.0514 0.0364 0.0152 0.0095
Hydrogenation rate % 60.47 69.76 78.59 91.06 94.41
Isooctyl alcohol Content % 97.80 97.85 97.89 98.07 97.95
Yield % 100.2 100.3 100.3 100.5 100.4

Claims (6)

1, a kind of by containing 2-ethyl-1-hexanal, the thick 2-ethyl of 2-ethyl-2-alkene-1-hexanol-1-hexanol hydrogenation mixture is made the method for 2-ethyl-1-hexanol, it is characterized in that having used liquid phase hydrogenating catalyst, described catalyst activity component is a nickel, carrier is an aluminum oxide, and optionally contain alkaline-earth metal as promotor, the weight content of alumina catalyst support is 60～95% in the catalyzer, the weight content of nickel counts 5～35% with NiO, the weight content of alkaline-earth metal counts 0～15% with its oxide compound, the liquid-phase hydrogenatin temperature is 80～260 ℃, and liquid-phase hydrogenatin pressure is normal pressure～6.0MPa.
2, method according to claim 1 is characterized in that the thing of alumina catalyst support is θ-Al mutually 2O 3Phase and γ-Al 2O 3Phase can also optionally contain a spot of α-Al 2O 3Phase.
3, method according to claim 1, the weight content that it is characterized in that alumina catalyst support in the catalyzer is 75～90%.
4, method according to claim 1 is characterized in that described alkaline-earth metal is that magnesium is or/and calcium.
5, method according to claim 1 is characterized in that active ingredient and the promotor in the described catalyzer loads on the alumina supporter with pickling process.
6, method according to claim 1, the specific surface area that it is characterized in that described catalyzer is at 110m 2More than/the g.
CN 02151550 2002-12-31 2002-12-31 Isooctanol refining process and its catalyst Expired - Lifetime CN1217899C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0508693B1 (en) * 2004-03-16 2014-10-29 Mitsubishi Chem Corp PROCESS FOR PRODUCTION OF PURIFIED ALCOHOLS
CN100415369C (en) * 2004-08-04 2008-09-03 中国石油化工股份有限公司 Coarse octyl alcohol liquid phase hydrogenation refining catalyst and hydrogenation reaction technique thereof
DE102005035816A1 (en) * 2005-07-30 2007-02-01 Oxeno Olefinchemie Gmbh Catalyst, useful for hydrogenating ester containing aldehyde mixture to their corresponding alcohols, comprises an aluminum oxide as substrate and nickel and/or cobalt as hydrogenation active component
CN102716748B (en) * 2012-06-19 2014-05-14 吉林大学 Catalyst used in pseudocumene hydrogenation reaction for producing BTX aromatic hydrocarbon and preparation method thereof
CN111068684B (en) * 2018-10-22 2023-10-20 中国石油化工股份有限公司 Coarse octanol liquid phase hydrogenation catalyst and preparation method thereof
CN114082421A (en) * 2021-10-26 2022-02-25 北京化工大学 Hydrogenation catalyst, preparation method thereof and application thereof in hydrogenation of isooctylaldehyde
CN116041159A (en) * 2021-10-28 2023-05-02 中国石油化工股份有限公司 Method for preparing isooctyl aldehyde
CN116041143A (en) * 2021-10-28 2023-05-02 中国石油化工股份有限公司 Process for preparing octanol

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