CN1072524C - Catalyst for making 1, 4 -butanediol by gas phase hydrogenation - Google Patents

Catalyst for making 1, 4 -butanediol by gas phase hydrogenation Download PDF

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Publication number
CN1072524C
CN1072524C CN 96120650 CN96120650A CN1072524C CN 1072524 C CN1072524 C CN 1072524C CN 96120650 CN96120650 CN 96120650 CN 96120650 A CN96120650 A CN 96120650A CN 1072524 C CN1072524 C CN 1072524C
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catalyzer
butyleneglycol
ester
maleic anhydride
catalyst
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CN 96120650
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CN1182639A (en
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王海京
冯薇荪
童立山
周怡然
高国强
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

The present invention relates to a catalyst for preparing 1, 4-butanediol from maleic anhydride and/or ester thereof by way of gas-phase hydrogenation. The catalyst has the following composition: CuCr<a>Zn<b>Ti<c>Ox, wherein a=0.7 to 1.5, b=0.05 to 1.2, c=0.1 to 1.0, and x represents the number of oxygen atoms corresponding to every metallic valence state. When the gas phase volume air speed of the maleic anhydride and/or the ester thereof reaches 100h<-1>, the catalyst improves the conversion rate of anhydride and/or ester thereof to be higher than 99 mol%, and increases the selectivity to 1, 4-butanediol to be higher than 80.0 mol%.

Description

A kind of gas phase hydrogenation system 1, the catalyzer of 4-butyleneglycol
The invention relates to MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1, the catalyzer of 4-butyleneglycol more particularly, the invention relates to the MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1 that contain Cu, Cr, Zn and Ti, the catalyzer of 4-butyleneglycol.
MALEIC ANHYDRIDE and ester shortening system 1 thereof, the technology of 4-butyleneglycol are since the sixties succeed in developing, and be few with reactions steps, investment is low, can regulate the characteristics of products therefrom and enjoy and gaze at.Early stage MALEIC ANHYDRIDE gas phase hydrogenation method adopts Zn-Cu-Cr catalyzer (special public clear 44-32567) and CuO-BeO-ZnO catalyzer (special public clear 47-23294), but can only obtain gamma-butyrolactone and can not directly obtain 1, the 4-butyleneglycol, and to obtain 1, the 4-butyleneglycol can only be by means of the catalyzer that contains the VII subgroup element, liquid-phase hydrogenatin by MALEIC ANHYDRIDE realizes (spy opens clear 51-133212), but the needed reaction pressure height of liquid-phase hydrogenatin technology (for example reaches 200Kg/cm 2), cause facility investment and process cost height.The diester of having developed maleic acid afterwards in the presence of copper chromite catalyst, gas-phase catalytic hydrogenation system 1, the technology of 4-butyleneglycol (spy opens clear 61-22035), and this arts demand is converted into diester in advance with MALEIC ANHYDRIDE, has increased reactions steps.
Japanese patent laid-open 2-25434 has proposed to use MALEIC ANHYDRIDE and/or succinyl oxide through gas phase hydrogenation system 1, the method for 4-butyleneglycol, and reaction is a catalyzer with the ZnO-CuO after reducing, at 180-280 ℃, 20～70 kg/cm 2Following enforcement, product is 1,4-butyleneglycol and tetrahydrofuran (THF) etc.When being reaction raw materials with the MALEIC ANHYDRIDE, gamma-butyrolactone is the solvent of reaction raw materials acid anhydride, is 1: 4 acid anhydride and ester charging with mol ratio, and the mol ratio of hydrogen and acid anhydride, ester is 1: 200 o'clock, 230 ℃, 40 kg/cm 2Under the condition, it is 9000 o'clock as the gaseous phase volume air speed -1(value under the normal temperature and pressure, down together; The gaseous phase volume air speed that this value is converted into acid anhydride is 9 o'clock -1), then the transformation efficiency of acid anhydride and ester is respectively 100% and 25.2%, for the charging total mole number, and 1,4-butyleneglycol productive rate is 31.9% (1, the selectivity of 4-butyleneglycol is 93.5%).
Japanese patent laid-open 2-233630 disclose a kind of in the presence of Cu-Cr or Cu-Cr-A (A is selected from Ba, Zn, Mn-Ba or Mn-Ba-Si) catalyzer the method for vapour phase hydrogenation MALEIC ANHYDRIDE, be reflected at 170-280 ℃, 10-100 kg/cm 2Under carry out, for example be that reaction raw materials, hydrogen acid anhydride mol ratio are that 600: 1, gaseous phase volume air speed are 4800 o'clock with the MALEIC ANHYDRIDE -1, (quite during the gaseous phase volume air speed 8 of acid anhydride -1) time, 220 ℃, 60 kg/cm 2Under the condition, the acid anhydride transformation efficiency is 100%, 1, and the selectivity of 4-butyleneglycol is 80.6%.
EP0373947A discloses the catalyzer of a kind of Cu-Cr-Mn of containing, can be used for gas phase hydrogenation system 1, the 4-butyleneglycol.This patent example 1 is a catalyzer with Cu, Cr, Mn oxide compound, 180 ℃, 40 kg/cm 2(the gaseous phase volume air speed of raw material acid anhydride is 22.5 o'clock down -1) time, the transformation efficiency of acid anhydride is 100 moles of %, 1, and 4-butyleneglycol selectivity is 60.5 moles of %.
In a word, existing MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1 of being used for, the catalyzer of 4-butyleneglycol can both make transformation efficiency reach almost 100 moles of % in certain raw material air speed scope, but 1, the selectivity of 4-butyleneglycol but raises and decline rapidly with the air speed of raw material, when the gaseous phase volume air speed of raw material acid anhydride is increased to 20 -1When above, 1 of none existing catalyzer, 4-butyleneglycol select performance to reach 80 moles of %.
The object of the present invention is to provide a kind of MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1 of being used for, the catalyzer of 4-butyleneglycol, this catalyzer can be at 20 o'clock -1Under the above raw material air speed raw material is transformed fully, make 1 simultaneously, the selectivity of 4-butyleneglycol is not less than 80 moles of %.
It is active ingredient that the present invention adopts Cu, Cr, Zn, Ti, the composite oxides that obtain through carrying out co-precipitation with alkali are catalyzer, this catalyzer is for the gas phase hydrogenation system 1 of MALEIC ANHYDRIDE and/or its ester, 4-butyleneglycol process has excellent catalytic performance, under the raw material air speed more much higher than prior art, this catalyzer makes the transformation efficiency of acid anhydride and/or ester reach 99 moles more than the %, 1, and the selectivity of 4-butyleneglycol reaches 80 moles more than the %.
Specifically, catalyzer of the present invention has following composition:
CuCr aZn bTi cO x
A=0.7～1.5 wherein, b=0.05～1.2, c=0.1～1.0, x is the corresponding oxygen atomicity that satisfies each atoms metal valence state.
Catalyzer of the present invention makes with coprecipitation method, that is: the precursor with Cu, Cr, Zn and Ti is scattered in the deionized water in required ratio, in room temperature, stir under with alkali precipitation to pH5.0～8.0, filter then, wash, collecting precipitation was 100～120 ℃ of dryings 2～6 hours; 400～550 ℃ of following roastings 2～25 hours, promptly get catalyzer again.
The precursor of the Cu that uses among the present invention, Cr, Zn and Ti can be their soluble salt, for example nitrate, vitriol or hydrochloride etc., and wherein preferred their nitrate, described Ti, Cr precursor also can adopt TiO 2, CrO 3
The alkali that adopts among the present invention can be alkali metal hydroxide, also can be ammoniacal liquor, wherein preferred ammoniacal liquor.
Catalyzer of the present invention needs to carry out prereduction before use, and reductive agent can adopt H 2, reducing gas such as CO, also can be with inert gas dilution reducing gas.Reduction can be undertaken by the method for known technology, for example under 1.0～3.0MPa pressure, every milliliter of catalyzer is fed reducing gas with the flow velocity of 120～200 ml/min, 300 ℃ of following reductase 12～5 hour.
The reaction raw materials that is applicable to catalyzer of the present invention can be MALEIC ANHYDRIDE and/or its single, double ester.Acid anhydride and/or ester raw material dissolve in The suitable solvent during charging, in gamma-butyrolactone or tetrahydrofuran (THF).
Use catalyzer of the present invention to carry out MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1, during the 4-butyleneglycol, suitable temperature of reaction is 180-300 ℃, and reaction pressure is 1～10MPa, and the mol ratio of hydrogen and acid anhydride and/or ester is 200～450: 1.
Adopt catalyzer of the present invention to carry out the gas phase hydrogenation system 1 of MALEIC ANHYDRIDE and/or its ester, the 4-butyleneglycol can adopt than the much higher raw material air speed of prior art and obtains the high conversion and the product 1 of raw material, the highly selective of 4-butyleneglycol.In the gaseous phase volume air speed of MALEIC ANHYDRIDE and/or its ester up to 98 o'clock -1, the transformation efficiency of acid anhydride and/or ester still can reach 99 moles more than the %, and 1, the selectivity of 4-butyleneglycol can reach 80.0 moles more than the %.Catalyzer of the present invention also can be higher than at 98 o'clock -1Unstripped gas phase volume air speed under operate, at this moment certain 1, the selectivity of 4-butyleneglycol can decrease.
Further specify the present invention below by embodiment, but not thereby limiting the invention.In all embodiment and comparative example, the gas phase air speed of MALEIC ANHYDRIDE and/or its ester is all amounted to into MALEIC ANHYDRIDE value (at this moment, the density of MALEIC ANHYDRIDE is 1.48 grams per milliliters) at normal temperatures and pressures.Catalyst metal is formed with X-ray fluorometry mensuration, and the reaction after product distributes with gc analysis (PEG20000 packed column, FID detects).
Embodiment 1～4 explanation Preparation of catalysts of the present invention
Embodiment 1
With 26.1 gram Cu (NO 3) 23H 2O (Beijing Chemical Plant produces, chemical pure), 6.4 gram Zn (NO 3) 26H 2O (Beijing Chemical Plant produces, chemical pure), 8.8 gram CrO 3(Beijing Chemical Plant produces, chemical pure), 3.5 gram TiO 2(Beijing Chemical Plant produces, chemical pure) is dissolved in 280 ml deionized water, (Beijing Chemical Plant produces to add ammoniacal liquor under room temperature, stirring, the heavy % of concentration 23-25), until pH5.4 ± 0.2, filter, washing, collecting precipitation, 120 ℃ of dryings 6 hours,, obtain catalyst A: CuCr 550 ℃ of roastings 24 hours 0.8Zn 0.2Ti 0.4O 3.2(oxygen level is a calculated value, down together).
Embodiment 2
With 26.1 gram Cu (NO 3) 23H 2O, 3.2 gram Zn (NO 3) 26H 2O, 10.8 gram CrO 3, 1.8 the gram TiO 2Be dissolved in 300 ml deionized water, under room temperature, stirring, precipitate,, handle by the mode of embodiment 1 then, obtain catalyst B: CuCrZn until pH5.0 ± 0.2 with ammoniacal liquor 0.1Ti 0.2O 3.0
Embodiment 3
With 52.0 gram Cu (NO 3) 23H 2O, 64.0 gram Zn (NO 3) 26H 2O, 28.0 gram CrO 3, 11.0 the gram TiO 2Be dissolved in 2000 ml deionized water, under room temperature, stirring, precipitate,, handle by the mode of embodiment 1 then, obtain catalyzer C:CuCr until pH5.0 ± 0.2 with ammoniacal liquor 1.3Zn 1.0Ti 0.6O 5.15
Embodiment 4
With 26.1 gram Cu (NO 3) 23H 2O, 9.6 gram Zn (NO 3) 26H 2O, 9.7 gram CrO 3, 2.2 the gram TiO 2Be dissolved in 600 ml deionized water, under room temperature, stirring, precipitate,, handle by the mode of embodiment 1 then, obtain catalyzer D:CuCr until pH7.2 ± 0.2 with ammoniacal liquor 0.9Zn 0.3Ti 0.25O 3.15
Comparative example 1
Open with the spy that embodiment 1 is a comparative example among the flat 2-233630, its catalyzer is decided to be A ＇, A ＇ has following general formula and forms: CuCr 1.4Mn 0.11Ba 0.1O 5.32
Comparative example 2
Open with the spy that embodiment 9 is a comparative example among the flat 2-233630, its catalyzer is decided to be B ', B ＇ has following general formula and forms: CuCr 2Ba 0.05O 4.05
Embodiment 5～8 explanations catalyzer of the present invention is used for catalyzed gas hydrogenation system 1, during the 4-butyleneglycol, and the excellent properties that shows.
Embodiment 5
Get 3.2 milliliters of 26～40 order catalyst A and pack in 8 millimeters of diameters, long 400 millimeters the stainless steel tubular type reactor, under 2.0MPa pressure, feed pure hydrogen, 300 ℃ of reduction 4 hours with 500 ml/min flow velocitys.Bed temperature is transferred to 240 ℃, pressure transfer to 7.0MPa, the stable back charging of system, charging is that mol ratio is 1: 1: 1 MALEIC ANHYDRIDE (MAN), gamma-butyrolactone (GBL) and a butanols (BuOH), wherein MAN is a reaction raw materials, GBL and butanols are the raw material solvent, hydrogen acid anhydride mol ratio is 170: 1 during reaction, and MAN gaseous phase volume air speed is 98.6 o'clock -1, reaction result sees Table 2.
Embodiment 6
Get catalyst B, operate by the mode of embodiment 5, that different is the MAN and the GBL of mol ratios such as reaction feed is, temperature is that 220 ℃, pressure are 6.0MPa, and hydrogen acid anhydride mol ratio is 360: 1, and the gaseous phase volume air speed of MAN is 34 o'clock -1, reaction result sees Table 2.
Embodiment 7
Get catalyzer C, react by the condition of embodiment 6, temperature of reaction that different is is that 225 ℃, reaction pressure are 4.0MPa, and hydrogen acid anhydride mol ratio is 372: 1, and the gaseous phase volume air speed of MAN is 34 o'clock -1, reaction result sees Table 2.
Embodiment 8
Get catalyzer D, react by the condition of embodiment 5, temperature of reaction that different is is that 219 ℃, reaction pressure are 4.7MPa, and hydrogen acid anhydride mol ratio is 300: 1, and the gaseous phase volume air speed of MAN is 34 o'clock -1, reaction result sees Table 2.
Comparative example 3
Get catalyst A ', operate by the mode of embodiment 5, temperature of reaction that different is is that 230 ℃, reaction pressure are 4.0MPa, reaction feed is that mol ratio is 1: 1 MAN and GBL, hydrogen acid anhydride mol ratio is 400: 1, MAN gaseous phase volume air speed is 23.9 o'clock -1, reaction result sees Table 2.
Comparative example 4
Get catalyst B ', operate by the mode of embodiment 5, that different is 220 ℃ of temperature of reaction, reaction pressure 6.0MPa, hydrogen acid anhydride mol ratio is 600: 1, MAN gaseous phase volume air speed is 10.2 o'clock -1, reaction result sees Table 2.
Table 1
The catalyzer numbering Catalyzer is formed
Embodiment 1 A CuCr 0.8Zn 0.2Ti 0.4O 3.2
Embodiment 2 B CuCrZn 0.1Ti 0.2O 3.0
Embodiment 3 C CuCr 1.3Zn 1.0Ti 0.6O 5.15
Embodiment 4 D CuCr 0.9Zn 0.3Ti 0.25O 3.15
Comparative example 1 A＇ CuCr 1.4Mn 0.11Ba 0.1O 5.32
Comparative example 2 B′ CuCr 2Ba 0.05O 4.05
Table 2
Example 5 Example 6 Example 7 Example 8 Comparative example 3 Comparative example 4
The catalyzer numbering A B C D A′ B′
Temperature of reaction, ℃ 240 220 225 219 230 220
Reaction pressure, MPa 7.0 6.0 4.0 4.7 4.0 6.0
MAN/GBL, mole 1∶1∶1 * 1∶1 1∶1 1∶1∶1 * 1∶1 MAN **
H 2/ MAN, mole 170∶1 360∶1 372∶1 300∶1 400∶1 600∶1
When MAN gaseous phase volume sky selects -1 98.6 34 34 34 23.9 10.2
The MAN transformation efficiency, mole % ＞99 ＞99 ＞99 ＞99 100 100
Selectivity, mole % 1, the 4-butyleneglycol 91.3 93.0 80.1 90.8 50.1 80.6
Tetrahydrofuran (THF) 5.7 5.2 13.6 6.8 39.1 16.3
Butanols 2.9 1.8 6.1 2.4 1.2 -
*This ratio is MAN: GBL: BuOH=1: 1: 1
*Directly make raw material herein with MAN

Claims (10)

  1. One kind be used for MALEIC ANHYDRIDE and/or its ester gas phase hydrogenation system 1,4 butyleneglycol contain Cu, Cr, Zn catalyzer, it is characterized in that it has following composition:
    CuCr aZn bTi cO x
    A=0.7～1.5 wherein, b=0.05～1.2, c=0.1～1.0, x is the corresponding oxygen atomicity that satisfies each atoms metal valence state.
  2. 2. by the catalyzer of claim 1, it is characterized in that it is made through co-precipitation in the presence of alkali by the precursor of Cu, Cr, Zn and Ti.
  3. 3. by the catalyzer of claim 2, it is characterized in that the soluble salt of the precursor of said Cu, Cr, Zn and Ti for each element.
  4. 4. by the catalyzer of claim 3, it is characterized in that the nitrate of the precursor of said Cu, Cr, Zn and Ti for each element.
  5. 5. by the catalyzer of claim 2, the precursor that it is characterized in that said Ti is TiO 2
  6. 6. by the catalyzer of claim 2, the precursor that it is characterized in that said Cr is CrO 3
  7. 7. by the catalyzer of claim 2, it is characterized in that said alkali is alkali metal hydroxide.
  8. 8. by the catalyzer of claim 2, it is characterized in that said alkali is ammoniacal liquor.
  9. 9. by the catalyzer of claim 2, the pH that it is characterized in that said co-precipitation is 5.0～8.0.
  10. 10. the catalyzer of claim 1 is used for the gas phase hydrogenation system 1 of MALEIC ANHYDRIDE and/or its ester, 4-butyleneglycol.
CN 96120650 1996-11-15 1996-11-15 Catalyst for making 1, 4 -butanediol by gas phase hydrogenation Expired - Fee Related CN1072524C (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10225929A1 (en) 2002-06-11 2003-12-24 Basf Ag Two-stage process for the production of butanediol with intermediate separation of succinic anhydride
DE10225927A1 (en) 2002-06-11 2003-12-24 Basf Ag Process for the production of butanediol by combined gas phase and liquid phase synthesis
TWI564072B (en) 2011-11-09 2017-01-01 China Petrochemical Technology Co Ltd Hydrogenation catalyst and preparation method thereof
CN102952009B (en) * 2012-08-06 2015-07-22 刘长宝 Method, technology and production line for producing succinic acid and 1,4-butanediol by use of ethylene glycol
CN108114727B (en) * 2016-11-28 2020-08-11 中国石油化工股份有限公司 Hydrogenation catalyst, preparation method and application thereof

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