CN104857981B - A kind of metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol and its preparation method and application - Google Patents

A kind of metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol and its preparation method and application Download PDF

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CN104857981B
CN104857981B CN201510201600.9A CN201510201600A CN104857981B CN 104857981 B CN104857981 B CN 104857981B CN 201510201600 A CN201510201600 A CN 201510201600A CN 104857981 B CN104857981 B CN 104857981B
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acetic acid
isopropanol
metal nitride
atmosphere
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CN104857981A (en
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李德宝
郭荷芹
肖勇
侯博
贾丽涛
陈从标
鲁怀乾
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

A kind of metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol is made up of the nitride, promoter metal nitride and carrier of iron, and a mole composition for catalyst is：Iron in nitrided iron：Metal in promoter metal nitride：Carrier=8 25：3‑10：100.The present invention is simple with isopropanol synthesis technique flow, the free from corrosion advantage of equipment.

Description

The metal nitride catalyst and its preparation method of a kind of acetic acid hydrogenation synthesis isopropanol and Using
Technical field
The present invention relates to a kind of catalyst of petrohol and its preparation method and application, specifically one kind is used for acetic acid Nitride metal catalyst of hydrogenation synthesis isopropanol and its preparation method and application.
Background technology
Isopropanol (Isopropyl Alcohol, abbreviation IPA) also known as IPA, dimethylcarbinol, are a kind of function admirables Organic solvent, or the important intermediate of a variety of organic compounds of production can be used as synthetic glycerine, isopropyl acetate and third The raw material of ketone etc., oil-fired antifreeze additive is also widely used as, for automobile and aviation fuel etc..In addition, isopropyl Alcohol can also be used to manufacture bactericide, insecticide, cleaning agent and disinfection preservative etc..In agricultural chemicals, electronics industry, medicine, coating, day Have been widely used with the fields such as chemical industry and organic synthesis tool, exploitation prospect is wide.
The production method of industrial isopropanol is mainly propylene hydration method and acetone hydrogenation method.Propylene hydration method can be divided into third Two kinds of alkene indirect hydration method and direct hydration method.Propylene indirect hydration method is propylene to be dissolved in sulfuric acid solution esterification occurs instead Isopropyl acid sulphate and sulfuric acid diisopropyl ester should be generated, then through hydrolysis, is refining to obtain isopropanol.The method flow is complicated, selectivity Relatively low, equipment corrosion is serious, and waste water and exhaust-gas treatment are more difficult, is gradually eliminated after the 1980s.The direct water of propylene Legal is to make propylene that hydration reaction generation isopropanol, while by-product normal propyl alcohol directly occur in the presence of a catalyst, is current work The main method of isopropanol is produced in industry.Due to state's inner propene resource scarcity, the production cost of propylene hydration method petrohol It is high.Acetone hydrogenation method petrohol uses copper or zinc oxide as carried catalyst or nickel-base catalyst, 70~ 200 DEG C, under condition of normal pressure, acetone hydrogenation generation isopropanol, acetone gas phase hydrogenation such as CN201110293568.3 announcements can be divided into A kind of method of cupro-nickel base catalyst acetone gas phase hydrogenation petrohol；Liquid-phase hydrogenatin such as CN201110300319.4 A kind of method of nickel-base catalyst catalysis acetone liquid-phase hydrogenatin petrohol is disclosed, US7799958 discloses acetone liquid phase The method of hydrogenation synthesis isopropanol, acetone liquid-phase hydrogenatin is converted into by isopropanol by least two hydrogenation reaction stage.Acetone solution Mutually hydrogenation petrohol reaction pressure is high, and equipment investment is big, and cost is high, and gas phase hydrogenation petrohol reacts the effect that must exchange heat Rate is low, and in industrial production, heat of reaction can not remove, poor operability.
The content of the invention
It is an object of the invention to provide a kind of catalyst for the step hydrogenation synthesis isopropanol of acetic acid one and its preparation side Method and application, to solve existing isopropanol synthesis technique long flow path, the problem of equipment corrosion is serious.
The catalyst of the present invention is made up of the nitride, promoter metal nitride and carrier of iron, mole composition of catalyst For：Iron in nitrided iron：Metal in promoter metal nitride：Carrier=8-25：3-10：100.
Promoter metal nitride as described above is cobalt nitride, nickel oxide, molybdenum nitride, the one or more in tungsten nitride.
Carrier as described above is zirconium dioxide, silica, alundum (Al2O3) or titanium dioxide etc., preferably nano-silica Change zirconium, nano silicon, γ-Al2O3Or anatase titania
Method for preparing catalyst provided by the invention is：
(1) ferric nitrate and soluble promoter metal compound are added in deionized water, stirring is completely dissolved it, obtains To solution A；
(2) carrier is added into solution A, in 30-60 DEG C impregnate 2-10h, 80-120 DEG C of dry 10-24h, 400-600 DEG C 4-6h is calcined, obtains load metal oxide；
(3) by load metal oxide in pure NH3550-750 DEG C is warming up to 0.5-3 DEG C/min speed in atmosphere, And 3-8h is nitrogenized at this temperature, nitridation air speed is 6000-15000h-1, after the completion of nitridation, the 3000- in ammonia atmosphere 7000h-1After being down to room temperature, O is passed through2Content is 0.5v%-2.5v% O2It is with the gaseous mixture of inert gas, its surface is blunt Change, that is, obtain metal nitride catalyst.
In step (1) as described above, described soluble promoter metal compound is cobalt nitrate, cobalt acetate, nickel nitrate, four Ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, ammonium phosphotungstate.
In nitride preparation method as described above, it is characterised in that described inert atmosphere is N2, in He, Ar one Kind.
The present invention catalyst application process be：
Above-mentioned catalyst is applied to fixed bed reactors：In H before reaction2It is warming up under atmosphere with 0.5-3 DEG C/min 400-600 DEG C, and 3-6h is reduced at this temperature, H2Gas space velocity is 2000-7000h-1, H2Atmosphere drops to reaction temperature 250-330 DEG C, it is passed through and is preheated to 130~180 DEG C of acetic acid steam and H2Hybrid reaction gas, acetic acid steam is in hybrid reaction gas In shared volume composition be 5~50v%, reaction gas air speed is 2000-5000ml/gcat.h, operating pressure is 3.0~5.0MPa.
The present invention compared to the prior art the advantages of be：
1) catalyst is cheap, and preparation method is simple, easy to operate.
2) reaction process flow is short, and production isopropanol cost is low.
3) reaction condition is gentle, acetic acid high conversion rate, and isopropanol selectivity is high.
Embodiment：
The present invention will be invented by following embodiments below, but the present invention is not limited in these examples.
Embodiment 1
By 3.23g Fe (NO3)2.9H2O and 1.45g Co (NO3)2.6H2O is dissolved in 12.0ml deionized waters, and stirring makes it It is completely dissolved.12.32g nanometers ZrO is added into above-mentioned solution2, 30 DEG C of dippings 10h, 100 DEG C of dry 16h, 500 DEG C are calcined 5h, Obtain FeCoOx/ZrO2。
The FeCoO that will be obtainedx/ZrO2In NH3550 DEG C are warming up to 0.5 DEG C/min in atmosphere, and is nitrogenized at this temperature 8h, nitridation air speed are 15000h-1.After the completion of nitridation, in 7000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 1.0v% O2With N2Its surface passivation is obtained ZrO by the mixed gas of composition2The iron cobalt nitride catalyst of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2Under atmosphere 500 are warming up to 1 DEG C/min DEG C, and 4h is reduced at this temperature, H2Gas space velocity is 3000h-1, H2Atmosphere drops to 280 DEG C of reaction temperature, is passed through and is preheated to 150 DEG C of acetic acid steam and H2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 30v%, reaction gas air speed For 2000ml/gcat.h, operating pressure 3.0MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 2
By 4.04g Fe (NO3)2.9H2O、1.45g Co(NO3)2.6H2O and 0.87g Ni (NO3)2.6H2O is dissolved in 6.5ml In deionized water, stirring is completely dissolved it.6.0g Nano-meter SiO_2s are added into above-mentioned solution2, 40 DEG C of dipping 8h, 120 DEG C of dryings 12h, 600 DEG C of roasting 4h, obtains FeCoNiOx/SiO2。
The FeCoNiO that will be obtainedx/SiO2In NH3600 DEG C are warming up to 1 DEG C/min in atmosphere, and is nitrogenized at this temperature 6h, nitridation air speed are 10000h-1.After the completion of nitridation, in 5000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 2.5v% O2Its surface passivation is obtained SiO by the mixed gas with Ar compositions2The iron-cobalt-nickel nitride catalyst of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2Under atmosphere 500 are warming up to 2 DEG C/min DEG C, and 4h is reduced at this temperature, H2Gas space velocity is 2500h-1, H2Atmosphere drops to 290 DEG C of reaction temperature, is passed through and is preheated to 140 DEG C of acetic acid steam and H2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 20v%, reaction gas air speed For 3000ml/gcat.h, operating pressure 3.5MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 3
By 6.01g Fe (NO3)2.9H2O and 0.87g Ni (NO3)2.6H2O is dissolved in 11.5ml deionized waters, and stirring makes it It is completely dissolved.12.32g nanometers ZrO is added into above-mentioned solution2, 50 DEG C of dippings 4h, 80 DEG C of dry 24h, 400 DEG C of roasting 6h, obtain To FeNiOx/ZrO2。
The FeNiO that will be obtainedx/ZrO2In NH3750 DEG C are warming up to 2 DEG C/min in atmosphere, and nitrogenizes 3h at this temperature, Nitridation air speed is 6000h-1.After the completion of nitridation, in 3000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 0.5v% O2Its surface passivation is obtained ZrO by the mixed gas with He compositions2The iron nickel nitride catalyst of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2It is warming up under atmosphere with 0.5 DEG C/min 400 DEG C, and 6h is reduced at this temperature, H2Gas space velocity is 4000h-1, H2Atmosphere drops to 260 DEG C of reaction temperature, is passed through pre- The acetic acid steam and H of heat to 130 DEG C2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 50v%, reaction gas Air speed is 6000ml/gcat.h, operating pressure 4.0MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 4
By 8.07g Fe (NO3)2.9H2O and 1.45g Ni (NO3)2.6H2O is dissolved in 6.0ml deionized waters, and stirring makes it It is completely dissolved.5.1g γ-Al are added into above-mentioned solution2O3, 60 DEG C of dippings 2h, 100 DEG C of dry 18h, 600 DEG C of roasting 4h, obtain FeNiOx/γ-Al2O3。
The FeNiO that will be obtainedx/γ-Al2O3In NH3600 DEG C, and nitrogen at this temperature are warming up to 3 DEG C/min in atmosphere Change 4h, nitridation air speed is 8000h-1.After the completion of nitridation, in 5000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 0.5v% O2With N2Its surface passivation is obtained γ-Al by the mixed gas of composition2O3The iron nickel nitride catalyst of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2Under atmosphere 600 are warming up to 3 DEG C/min DEG C, and 3h is reduced at this temperature, H2Gas space velocity is 5000h-1, H2Atmosphere drops to 310 DEG C of reaction temperature, is passed through and is preheated to 160 DEG C of acetic acid steam and H2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 10v%, reaction gas air speed For 7000ml/gcat.h, operating pressure 5.0MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 5
By 10.09g Fe (NO3)2.9H2O and 1.03g (NH4)2Mo2O7.4H2O is dissolved in 11.0ml deionized waters, and stirring makes It is completely dissolved.12.32g nanometers ZrO is added into above-mentioned solution2, 40 DEG C of dippings 6h, 120 DEG C of dry 12h, 500 DEG C of roastings 5h, obtain FeMoOx/ZrO2。
The FeMoO that will be obtainedx/ZrO2In NH3600 DEG C are warming up to 1.5 DEG C/min in atmosphere, and is nitrogenized at this temperature 5h, nitridation air speed are 8000h-1.After the completion of nitridation, in 5000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 1.0v% O2With N2Its surface passivation is obtained ZrO by the mixed gas of composition2The iron Molybdenum nitride catalysts of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2It is warming up under atmosphere with 1.5 DEG C/min 500 DEG C, and 4h is reduced at this temperature, H2Gas space velocity is 7000h-1, H2Atmosphere drops to 290 DEG C of reaction temperature, is passed through pre- The acetic acid steam and H of heat to 150 DEG C2Gaseous mixture, acetic acid steam shared volume composition in reaction gas be 5v%, reaction gas sky Speed is 4000ml/gcat.h, operating pressure 3.5MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 6
By 6.06g Fe (NO3)2.9H2O and 0.82g (NH4)2Mo2O7.4H2O is dissolved in 6.5ml deionized waters, and stirring makes it It is completely dissolved.6.0g Nano-meter SiO_2s are added into above-mentioned solution2, 40 DEG C of dippings 6h, 120 DEG C of dry 12h, 500 DEG C of roasting 5h, obtain To FeMoOx/SiO2。
The FeMoO that will be obtainedx/SiO2In NH3600 DEG C are warming up to 1.5 DEG C/min in atmosphere, and is nitrogenized at this temperature 5h, nitridation air speed are 8000h-1.After the completion of nitridation, in 5000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 1.5v% O2With N2Its surface passivation is obtained SiO by the mixed gas of composition2The iron Molybdenum nitride catalysts of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2Under atmosphere 400 are warming up to 2 DEG C/min DEG C, and 5h is reduced at this temperature, H2Gas space velocity is 3000h-1, H2Atmosphere drops to 330 DEG C of reaction temperature, is passed through and is preheated to 140 DEG C of acetic acid steam and H2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 20v%, reaction gas air speed For 3000ml/gcat.h, operating pressure 4.0MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 7
By 6.06g Fe (NO3)2.9H2O and 1.25g (NH4)3PW12O40.3H2O is dissolved in 13.0ml deionized waters, stirring It is completely dissolved it.12.32g nanometers ZrO is added into above-mentioned solution2, 40 DEG C of dippings 6h, 120 DEG C of dry 12h, 500 DEG C of roastings 5h, obtain FeWOx/ZrO2。
The FeWO that will be obtainedx/ZrO2In NH3600 DEG C are warming up to 1.5 DEG C/min in atmosphere, and is nitrogenized at this temperature 5h, nitridation air speed are 8000h-1.After the completion of nitridation, in 5000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 1.5v% O2Its surface passivation is obtained ZrO by the mixed gas with Ar compositions2The ferrotungsten nitride catalyst of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2Under atmosphere 450 are warming up to 2 DEG C/min DEG C, and 4h is reduced at this temperature, H2Gas space velocity is 3500h-1, H2Atmosphere drops to 290 DEG C of reaction temperature, is passed through and is preheated to 150 DEG C of acetic acid steam and H2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 20v%, reaction gas air speed For 2500ml/gcat.h, operating pressure 4.0MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Embodiment 8
By 6.06g Fe (NO3)2.9H2O and 1.5g H18N2O9W is dissolved in 12.5ml deionized waters, and stirring makes it completely molten Solution.8.0gTiO is added into above-mentioned solution2, 40 DEG C of dippings 6h, 120 DEG C of dry 12h, 500 DEG C of roasting 5h, obtain FeWOx/ TiO2。
The FeWO that will be obtainedx/TiO2In NH3600 DEG C are warming up to 1.5 DEG C/min in atmosphere, and is nitrogenized at this temperature 5h, nitridation air speed are 8000h-1.After the completion of nitridation, in 5000h-1NH3After being cooled to room temperature in atmosphere, O is passed through2Content is 1.5v% O2With N2Its surface passivation is obtained TiO by the mixed gas of composition2The ferrotungsten nitride catalyst of load.
Above-mentioned catalyst is applied to tubular fixed-bed reactor：In H before reaction2Under atmosphere 400 are warming up to 2 DEG C/min DEG C, and 5h is reduced at this temperature, H2Gas space velocity is 3000h-1, H2Atmosphere drops to 290 DEG C of reaction temperature, is passed through and is preheated to 150 DEG C of acetic acid steam and H2Gaseous mixture, acetic acid steam shared volume composition in reaction gas is 20v%, reaction gas air speed For 2500ml/gcat.h, operating pressure 3.5MPa.
Catalyst fixed bed reactivity worth is shown in Table 1.
Acetic synthesis isopropanol reaction performance on the nitride catalyst of table 1
As can be seen from Table 1, metal nitride catalyst provided by the invention can be catalyzed acetic acid conversion one-step synthesis isopropyl Alcohol, reaction condition is gentle, acetic acid high conversion rate, and isopropanol selectivity is high.
The foregoing is only the preferred embodiments of the present invention and oneself, be not intended to limit the invention, for the skill of this area For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies Change, equivalent substitution, improvement etc., should be included in the scope of the protection.

Claims (5)

  1. A kind of 1. metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol, it is characterised in that catalyst by iron nitride, Promoter metal nitride and carrier composition, a mole composition for catalyst are：Iron in nitrided iron：Gold in promoter metal nitride Category：Carrier=8-25：3-10：100；
    And prepare by the following method：
    （1）Ferric nitrate and soluble promoter metal compound are added in deionized water, stirring is completely dissolved it, obtains molten Liquid A；
    （2）Carrier is added into solution A, 2-10 h, 80-120 DEG C of dry 10-24 h, 400-600 DEG C of roasting are impregnated in 30-60 DEG C 4-6 h are burnt, obtain load metal oxide；
    （3）By load metal oxide in pure NH3In atmosphere 550-750 DEG C is warming up to 0.5-3 DEG C/min speed, and 3-8h is nitrogenized at a temperature of this, nitridation air speed is 6000-15000 h-1, after the completion of nitridation, the 3000-7000h in ammonia atmosphere-1 After being down to room temperature, O is passed through2Content is 0.5 v%-2.5 v% O2With the gaseous mixture of inert atmosphere, its surface passivation obtains Metal nitride catalyst；
    Described promoter metal nitride is cobalt nitride, nickel oxide, molybdenum nitride, the one or more in tungsten nitride；
    Described carrier is zirconium dioxide, silica, alundum (Al2O3) or titanium dioxide.
  2. A kind of 2. metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol as claimed in claim 1, it is characterised in that institute The carrier stated is nano zirconium dioxide, nano silicon, γ-Al2O3Or anatase titania.
  3. A kind of 3. metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol as claimed in claim 1, it is characterised in that institute State step（1）In soluble promoter metal compound be cobalt nitrate, cobalt acetate, nickel nitrate, ammonium tetramolybdate, ammonium heptamolybdate, tungsten Sour ammonium or ammonium phosphotungstate.
  4. A kind of 4. metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol as claimed in claim 1, it is characterised in that institute The inert atmosphere stated is N2, one kind in He, Ar.
  5. 5. a kind of metal nitride catalyst of acetic acid hydrogenation synthesis isopropanol as described in claim any one of 1-4 is answered With, it is characterised in that comprise the following steps：
    Catalyst is applied to fixed bed reactors：In H before reaction2Under atmosphere 400-600 DEG C is warming up to 0.5-3 DEG C/min, and 3-6h, H are reduced at this temperature2Gas space velocity is 2000-7000h-1, H2Atmosphere drops to 250-330 DEG C of reaction temperature, is passed through It is preheated to 130~180 DEG C of acetic acid steam and H2Hybrid reaction gas, acetic acid steam shared volume composition in hybrid reaction gas For 5~50v%, reaction gas air speed is 2000-5000ml/gcat.h, operating pressure is 3.0~5.0MPa.
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CN101428214A (en) * 2007-11-07 2009-05-13 中国科学院大连化学物理研究所 Uses of aluminum oxide supported noble metal catalyst in cellulose hydrogenation hydrolyzation
CN104190457A (en) * 2014-08-29 2014-12-10 中国科学院山西煤炭化学研究所 Catalyst in synthesis of isopropanol by virtue of hydrogenation of acetic acid and preparation method and application of catalyst

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Publication number Priority date Publication date Assignee Title
CN101428214A (en) * 2007-11-07 2009-05-13 中国科学院大连化学物理研究所 Uses of aluminum oxide supported noble metal catalyst in cellulose hydrogenation hydrolyzation
CN104190457A (en) * 2014-08-29 2014-12-10 中国科学院山西煤炭化学研究所 Catalyst in synthesis of isopropanol by virtue of hydrogenation of acetic acid and preparation method and application of catalyst

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