CN101032688A - Activator for producing glycol by catalytic hydrogenation method - Google Patents
Activator for producing glycol by catalytic hydrogenation method Download PDFInfo
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- CN101032688A CN101032688A CN 200710021418 CN200710021418A CN101032688A CN 101032688 A CN101032688 A CN 101032688A CN 200710021418 CN200710021418 CN 200710021418 CN 200710021418 A CN200710021418 A CN 200710021418A CN 101032688 A CN101032688 A CN 101032688A
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Abstract
The present invention is Ni catalyst prepared with Ni-Al alloy as skeleton and through surface treatment with hot alkali solution to eliminate Al of 8-30 %. The Ni catalyst is used in catalytic hydrogenation of glycol material with low ultraviolet ray transmission rate to raise its ultraviolet ray transmission rate. The Ni catalyst has proper strength suitable for use in fixed bed reactor, high catalytic activity and long service life, and the rectified glycol product has low aldehyde content and high ultraviolet ray transmission rate.
Description
Technical field
The catalyst of the refining ethylene glycol of a kind of catalytic hydrogenation method that the present invention relates to, with highly basic 80～100 ℃ down with the amorphous aluminum nickel alloy in aluminium react, the clearance of aluminium is between 8%～30%, making with the alumel is that skeleton supports, the Raney nickel of surface active, is used for fixing the micro organic impurity that a continuous catalytic hydrogenation is removed influences the ethylene glycol ultraviolet permeability.
Background technology
Ethene generates oxirane with the oxygen reaction under the silver catalyst effect, oxirane absorbs, resolves and absorb once more laggardly to go into the hydration reactor reaction and generate ethylene glycol and many ethylene glycol through water, reactant liquor steams operations such as ethylene glycol and the separation of many ethylene glycol through multiple-effect evaporation, rectifying and dewatering, rectifying, get the ethylene glycol product.The ethylene glycol product that adopts this technology to produce all can reach the purity more than 99.9%, can be used for the production of polyester fiber, but be difficult to express with content owing to exist to some extent in the product, the organic impurities that UV Absorption is arranged in wavelength is 220～350nm scope, this class impurity has influenced the product quality of polyester to some extent, as painted, the intensity of fiber of fiber, color of fiber etc.
A large amount of impurity that influence the ethylene glycol product quality that studies show that mainly are the inevitable oxidized byproducts that produces in the oxidizing process of ethene, these accessory substances are generally organic oxygen-containing compound, comprise organic compounds such as aldehyde, ketone, carboxylic acid, in these impurity, the aldehyde of carboxylic acid compound and band conjugated double bond can occur stronger absorption at the 220nm place as methacrylaldehyde, crotonaldehyde etc.; And aldehyde, ketone and cyclic diketones compounds can have bigger absorption at the 270nm place.Therefore, reduce the content of this type of impurity, can improve the transmitance of ethylene glycol product at 220～350nm wave-length coverage ultraviolet light, significant to the quality that improves ethylene glycol.
Patent WO 9958483 and U.S. Pat 3970711 have been introduced the glycol water (hydration reaction liquid) of handling lower ethylene glycol of ultraviolet permeability or ethylene oxide hydration reaction generation with active carbon, obtain the ultraviolet permeability 220nm of ethylene glycol greater than 76% after making absorption, 250nm is greater than 90%, and 275nm is greater than 92%.Though charcoal absorption can improve the ultraviolet permeability of ethylene glycol, because the adsorption capacity of acticarbon is very limited, effect obviously reduces after use a period of time, and active carbon regeneration difficulty, and the use cost height limits its industrial applications.
U.S. Pat 4647705 discloses and had a kind ofly dripped behind the strong base solution stirring reaction three days in the mixture of ethylene glycol and alumel, handles the method that polyester that the ethylene glycol that obtains can satisfy the producd fibers level requires.But this method is not suitable for large-scale continuous production, and alumel brings inconvenience for the follow-up purification that separates with the aluminium oxide of highly basic reaction generation and excessive alkali.
Load type metal catalyst has more regular form and certain intensity, but its activated centre is less relatively, has reduced catalytic activity.The Raney catalyst has that metal surface area is big, the active advantage such as good of hydrogenation activity high and low temperature, its preparation and use existing report widely, but its inherent feature (as easy efflorescence loss etc.) has limited the scope of application of traditional Raney catalyst.
U.S. Pat 4826799 and US4895994 have introduced the alloy powder of organic polymer, aluminium and catalyst kneaded and formed, divide two-section calcining in the temperature more than 850 ℃ in air, make the active Raney catalyst that is used for fixing bed of cavernous structure.But in calcination process, formed one deck alpha-alumina layer, reduced activity of such catalysts at catalyst surface.
German patent DE 4446907 has proposed a kind of method for making of hydrogenation Raney catalyst, is raw material with the alloy of aluminium and transition elements, is that polyethylene alcohol and water or the stearic mixture of 3000～6000g/mol assisted with molecular weight.But low-molecular-weight polyvinyl alcohol easily causes the ratio of catalyst mesopore less and reduce catalyst activity.
Summary of the invention:
The object of the present invention is to provide a kind of Raney nickel that can be used for the ethylene glycol material is carried out fixed bed hydrogenation.
Its technical scheme is:
Adopt the aluminium in the amorphous aluminum nickel alloy of 10%～15% sodium hydroxide solution and nickeliferous 50% to react, the clearance of aluminium is between 8%～30%, making with the alumel is that skeleton supports, the Raney nickel of surface active, is washed till neutrality through deionized water, preserves standby in absolute ethyl alcohol.Wherein the mass ratio of alumel and NaOH is 1: 0.8～0.25.
Use technological process shown in Figure 1, the catalyst that this method is made is used for the carbon-carbon double bond of low ultraviolet permeability ethylene glycol and the two key class trace impurity hydrogenation of carbon oxygen, has good catalytic activity and service life, the clearance of aluminium is about 13% catalyst and moves 3000h continuously and still keep stable catalytic effect, see Fig. 2, this hydrogenation liquid is after rectifying, and ultraviolet permeability is stabilized in 220nm＞90%, 275nm＞95%, 350nm＞99%.
Description of drawings
Fig. 1 continuous catalytic hydrogenation is made with extra care the ethylene glycol process chart
Fig. 2 discharging UV value is the catalyst operation stability relatively
(charging ethylene glycol content 85%, UV value: 220nm=52.9%, 275nm=86.0%, 350nm=95.9%)
The specific embodiment
Following example will be further specified the present invention, but therefore not limit the present invention.
Embodiment 1～2:
1. in the 500mL four-hole boiling flask of agitator, thermometer, condenser pipe is housed, adding 22.9g particle diameter is about the nickel alumin(i)um alloy of 1.6～2.0mm, drip the about 180ml of NaOH solution of mass fraction 10%, 80 ℃ of insulated and stirred 3h, after gas not had is emitted, be washed till neutrality with deionized water, make catalyst (a), in absolute ethyl alcohol, preserve stand-by.Measure the content of aluminium, the clearance that calculates aluminium is 30%.With catalyst (a) 8mL filling in the fixed bed of internal diameter 10mm, long 4cm, to the ethylene glycol of mass concentration 12.5% at 80 ℃ of bed temperatures, hydrogen pressure 0.05MPa, air speed 55h
-1Catalytic hydrogenation under the condition, the ethylene glycol cut is collected in hydrogenation reaction solution rectifying, gets the ethylene glycol product, and the uv transmittance of charging, discharging and product relatively sees Table 1.
2. as example 1, quality of glycol concentration is 100%, and reaction condition is 94 ℃ of bed temperatures, hydrogen pressure 0.35MPa, air speed 18h
-1, the uv transmittance of charging, discharging and product relatively sees Table 1.
Table 1 catalyst (a) compares the UV value of material catalytic hydrogenation front and back and product
Embodiment 3～4:
3. in the 500mL four-hole boiling flask of agitator, thermometer, condenser pipe was housed, adding the 30g particle diameter was the nickel alumin(i)um alloy of 2.0～3.0mm, added the 130mL deionized water, be warming up to 85 ℃, drip 15%NaOH solution 80mL, the control temperature is not higher than 95 ℃, stirring at low speed 1h, be incubated 93 ℃ ± 2 ℃, leave standstill 2h, drip 15%NaOH solution 40mL again, leave standstill 0.5h, be washed till neutrality with deionized water, make catalyst (b), in absolute ethyl alcohol, preserve stand-by.Measure the content of aluminium, the clearance that calculates aluminium is 25%.With catalyst (b) 12.5mL filling in the fixed bed of internal diameter 20mm, long 3cm, to the ethylene glycol of mass concentration 85% at 67 ℃ of bed temperatures, hydrogen pressure 0.25MPa, air speed 40h
-1Catalytic hydrogenation under the condition, the ethylene glycol cut is collected in hydrogenation reaction solution rectifying, gets the ethylene glycol product, and the uv transmittance of charging, discharging and product relatively sees Table 2.
4. as example 3, quality of glycol concentration is 12.5%, and reaction condition is 80 ℃ of bed temperatures, hydrogen pressure 0.15MPa, air speed 25h
-1, the uv transmittance of charging, discharging and product relatively sees Table 2.
Table 2 catalyst (b) compares material catalytic hydrogenation front and back and product UV value
Embodiment 5～6:
5. as example 3, getting particle diameter is the nickel alumin(i)um alloy 12.5g of 1.0～1.6mm, add the 55mL deionized water, be warming up to 85 ℃, drip 15%NaOH solution 20mL, the control temperature is not higher than 95 ℃, stirring at low speed 1h is incubated 93 ℃ ± 2 ℃, leaves standstill 2h, drip 15%NaOH solution 9.9mL again, make pellet type catalyst (c).Measure the content of aluminium, the clearance that calculates aluminium is 13%.With catalyst (c) 2mL filling in the fixed bed of internal diameter 10mm, long 4cm, to the ethylene glycol of mass concentration 85% at 73 ℃ of bed temperatures, hydrogen pressure 0.25MPa, air speed 35h
-1Catalytic hydrogenation under the condition, the ethylene glycol cut is collected in hydrogenation reaction solution rectifying, gets the ethylene glycol product, and the uv transmittance of charging, discharging and product relatively sees Table 3.
6. as example 5, quality of glycol concentration is 100%, and reaction condition is 85 ℃ of bed temperatures, hydrogen pressure 0.5MPa, air speed 10h
-1, the uv transmittance of charging, discharging and product relatively sees Table 3.
Table 3 catalyst (c) compares material catalytic hydrogenation front and back and product UV value
Embodiment 7～8
7. as example 5, the NaOH consumption changes 15mL and 7.5mL respectively into, makes catalyst (d), and the aluminium clearance is 8%.With catalyst (d) 2mL filling in the fixed bed of internal diameter 10mm, long 4cm, to the ethylene glycol of mass concentration 12.5% at 70 ℃ of bed temperatures, hydrogen pressure 0.15MPa, air speed 20h
-1Catalytic hydrogenation under the condition, the ethylene glycol cut is collected in hydrogenation reaction solution rectifying, gets the ethylene glycol product, and the uv transmittance of charging and discharging relatively sees Table 4.
8. as example 7, quality of glycol concentration is 100%, and reaction condition is 75 ℃ of bed temperatures, hydrogen pressure 0.25MPa, air speed 30h
-1The uv transmittance of charging and discharging relatively sees Table 4.
Table 4 catalyst (d) compares material catalytic hydrogenation front and back and product UV value
Claims (1)
1. the catalyst of the refining ethylene glycol of a catalytic hydrogenation method, it is characterized in that this catalyst is that skeleton supports with particle diameter 1～3mm alumel Ni40～50%, the sodium hydroxide solution on top layer 10～15% is 8～30% at the catalyst aluminium content that 80～100 ℃ of processing make, and wherein the mass ratio of alumel and NaOH is 1: 0.8～0.25.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200710021418 CN101032688A (en) | 2007-04-11 | 2007-04-11 | Activator for producing glycol by catalytic hydrogenation method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098439A (en) * | 2013-04-11 | 2014-10-15 | 中国科学院大连化学物理研究所 | Biomass glycol refining method |
| CN104418704A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | Method for refining glycol |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
| CN106140196A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | BYD Hydrogenation for the hydrogenation catalyst of BDO and BYD Hydrogenation for the method for BDO |
| CN106622096A (en) * | 2016-11-18 | 2017-05-10 | 上海迅凯新材料科技有限公司 | Nickel-based adsorbent for deep desulfurization and deodorization of isopropanol and preparation method and application thereof |
| EP3450420A4 (en) * | 2016-03-30 | 2020-01-01 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for increasing uv transmittance of ethylene glycol |
| CN110961111A (en) * | 2019-12-19 | 2020-04-07 | 常州大学 | Supported catalyst for ethylene glycol hydrofining and preparation method thereof |
| CN111644172A (en) * | 2019-09-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN112028742A (en) * | 2020-09-27 | 2020-12-04 | 联泓新材料科技股份有限公司 | Method for preparing polymer-grade ethylene glycol by using ethylene glycol prepared by ethylene oxide hydration method as raw material |
| CN115368213A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Crude glycol hydrofining agent and preparation method and application thereof |
-
2007
- 2007-04-11 CN CN 200710021418 patent/CN101032688A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098439A (en) * | 2013-04-11 | 2014-10-15 | 中国科学院大连化学物理研究所 | Biomass glycol refining method |
| CN104418704A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | Method for refining glycol |
| CN104418704B (en) * | 2013-08-27 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method of refining ethylene glycol |
| CN106140196B (en) * | 2015-04-22 | 2019-02-05 | 上海迅凯新材料科技有限公司 | BYD adds the method that hydrogen prepares the hydrogenation catalyst of BDO and BYD adds hydrogen to prepare BDO |
| CN106140196A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | BYD Hydrogenation for the hydrogenation catalyst of BDO and BYD Hydrogenation for the method for BDO |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
| EP3450420A4 (en) * | 2016-03-30 | 2020-01-01 | Changchun Meihe Science and Technology Development Co., Ltd. | Method for increasing uv transmittance of ethylene glycol |
| US10836696B2 (en) | 2016-03-30 | 2020-11-17 | The Coca-Cola Company | Method for increasing UV transmittance of ethylene glycol |
| CN106622096A (en) * | 2016-11-18 | 2017-05-10 | 上海迅凯新材料科技有限公司 | Nickel-based adsorbent for deep desulfurization and deodorization of isopropanol and preparation method and application thereof |
| CN111644172A (en) * | 2019-09-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN111644172B (en) * | 2019-09-09 | 2023-12-01 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN110961111A (en) * | 2019-12-19 | 2020-04-07 | 常州大学 | Supported catalyst for ethylene glycol hydrofining and preparation method thereof |
| CN110961111B (en) * | 2019-12-19 | 2022-07-26 | 常州大学 | Supported catalyst for ethylene glycol hydrofining and preparation method thereof |
| CN112028742A (en) * | 2020-09-27 | 2020-12-04 | 联泓新材料科技股份有限公司 | Method for preparing polymer-grade ethylene glycol by using ethylene glycol prepared by ethylene oxide hydration method as raw material |
| CN115368213A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Crude glycol hydrofining agent and preparation method and application thereof |
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Application publication date: 20070912 |