CN1137944A - Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation - Google Patents
Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation Download PDFInfo
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- CN1137944A CN1137944A CN 95106349 CN95106349A CN1137944A CN 1137944 A CN1137944 A CN 1137944A CN 95106349 CN95106349 CN 95106349 CN 95106349 A CN95106349 A CN 95106349A CN 1137944 A CN1137944 A CN 1137944A
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Abstract
The catalyst for preparing 1,4-butanediol by gas-phase hydrogenating maleic anhydride and/or its ester has the formula of CuCraMnbBacMdOx, where M is Al or Ti, a=0.1-2, b=0.05-1, c=0.05-1.5, d=0.05-1,5, and X is the number of oxygen atoms needed for satisfying the atom Valences of metals. When volume space speed of said gas is up to 90/hr, the transform rate of anhydride and/or ester is up to 100% and the selectivity of 1,4-butanediol is up to 80 mol% or more.
Description
The invention relates to maleic anhydride and/or its ester vapour phase hydrogenation system 1, the catalyst of 4-butanediol, more particularly, the invention relates to the maleic anhydride and/or its ester vapour phase hydrogenation system 1 that contain Cu, Cr, Mn, Ba and Al or Ti, the catalyst of 4-butanediol.
Maleic anhydride and ester catalytic hydrogenation system 1 thereof, the technology of 4-butanediol 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 catalyst (special public clear 44-32567) and CuO-BeO-ZnO catalyst (special public clear 47-23294), but can only obtain gamma-butyrolacton and can not directly obtain 1, the 4-butanediol, and to obtain 1, the 4-butanediol can only be by means of the catalyst 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 equipment investment and operating 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-butanediol (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-butanediol.Reaction is a catalyst with the ZnO-CuO after reducing, at 180-280 ℃, and the 20-70 kg/cm
2Following enforcement, product is 1,4-butanediol and oxolane etc.When being reaction raw materials with the maleic anhydride, gamma-butyrolacton 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 equivalent to acid anhydride is 9 o'clock
-1), then the conversion ratio of acid anhydride and ester is respectively 100% and 25.2%, and for the charging total mole number 1,4-butanediol productive rate is 31.9% (1, the selectivity of 4-butanediol 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) catalyst 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, (during raw material acid anhydride gaseous phase volume air speed 8
-1) time, 220 ℃, 60 kg/cm
2Under the condition, the acid anhydride conversion ratio is 100%, 1, and the selectivity of 4-butanediol is 80.6%.
Japanese patent laid-open 2-233632 adopts the copper Mn catalyst of reduction, and maleic anhydride and/or succinyl oxide are carried out vapour phase hydrogenation system 1, and the 4-butanediol is for example 220 ℃, 60 kg/cm
2, maleic anhydride and hydrogen mol ratio be that 1: 600, feeding gas phase volume air speed are 4800 o'clock
-1(the gaseous phase volume air speed of raw material maleic anhydride is 8 o'clock
-1) condition under, the maleic anhydride conversion ratio is 100%, 1,4-butanediol selectivity is 95.4%.
EP0373947A disclose a kind of in the presence of the CuO-CrO-MnO catalyst method of vapour phase hydrogenation maleic anhydride.This patent is pointed out, in CuO-CrO-MnO, add noble metal Re and then can under air speed is not very high situation, not improve 1, the selectivity of 4-butanediol, but will improve the cost of catalyst greatly like this, and when not having Re, then 1, the selectivity of 4-butanediol will descend, and be 9000 o'clock being 1: 1 acid anhydride and gamma-butyrolacton solvent with mol ratio as mol ratio 200: 1, the gaseous phase volume air speed of reaction feed, hydrogen and acid anhydride, ester for example
-1(the gaseous phase volume air speed of raw material acid anhydride is 22.5 o'clock
-1) time, 180 ℃, 40 kg/cm
2Down, no matter have or not Re in the catalyst, the conversion ratio of acid anhydride is 100%, but 1, the selectivity of 4-butanediol is 90.2% when Re exists; During no Re, selectivity reduces to 60.5%.
In a word, existing maleic anhydride and/or its ester vapour phase hydrogenation system 1 of being used for, the non-precious metal catalyst of 4-butanediol can both make conversion ratio reach almost 100% in certain raw material air speed scope, but 1, the selectivity of 4-butanediol 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 catalyst, 4-butanediol select performance to reach 80%.
The object of the present invention is to provide a kind of maleic anhydride and/or its ester vapour phase hydrogenation system 1 of being used for, the catalyst of 4-butanediol, this catalyst 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-butanediol is not less than 80%.
We find, Cu, Cr, Mn, Ba and the Al of employing special ratios or Ti are as active component, the composite oxide catalysts that obtains through carrying out co-precipitation with alkali, vapour phase hydrogenation system 1 at maleic anhydride and/or its ester, show excellent catalytic performance in the 4-butanediol process, adopt it can under the raw material air speed more much higher, obtain high conversion and high selectivity than prior art.
We find that also the increase of Al content helps product 1 in this composite oxide catalysts, and the 4-butanediol optionally improves, and the present invention has adopted the method for multiple step coprecipitation to prepare catalyst.
Specifically, catalyst of the present invention has following general formula composition:
CuCr
aMn
bBa
cM
dO
xWherein M is selected from Al and Ti:
A=0.1～2, b=0.05～1, c=0.05～1.5, d=0.01～1.5, x is the corresponding oxygen atomicity that satisfies each metallic atom valence state.
Catalyst of the present invention makes with coprecipitation, that is: the precursor with Cu, Cr, Mn, Ba and Al or Ti is scattered in the decationizing water, 20-70 ℃, stir under, use alkali precipitation, until pH6～8, ageing at room temperature 1～3 hour, filter then, wash, collecting precipitation was at 100～120 ℃ of dry 2-20 hours, at 300～600 ℃ of roasting 2-30 hours, promptly get catalyst.
When Al in the catalyst accounts for all metal component total mole numbers 20% when above, for keeping high catalytic activity to reach to 1, the selectivity of 4-butanediol, should adopt the method for multiple step coprecipitation to prepare catalyst, that is: with whole Ba, Al precursor and 1/3～1/2 Cu, Cr, the Mn precursor is scattered in the decationizing water, at 20-70 ℃, stir and add alkali down until pH9～10 formation slurries, then with remaining Cu, Cr, the dispersion liquid of Mn precursor in decationizing water is at 20-70 ℃, join in the above-mentioned slurries under stirring, co-precipitation is carried out in control pH6～8 (can add alkali in case of necessity).And then ageing is filtered, washing, dry, roasting.
The precursor of the Cu that uses among the present invention, Cr, Mn, Ba, Al or Ti can be metal soluble salt, for example nitrate, hydrochloride, preferably nitrate separately.Also can adopt CrO
3, Ba (OH)
2And TiO
2Respectively as the precursor of Cr, Ba and Ti.
Precipitating reagent alkali is selected from ammoniacal liquor and alkali metal hydroxide, preferred ammoniacal liquor.
Catalyst of the present invention needs to reduce in advance before use, and reducing agent can adopt H
2With reducibility gas such as CO, reduction can be at 1.0-6.0MPa pressure, carries out under 250～300 ℃, and the reducing gas flow is 50～200 ml/min with respect to every milliliter of catalyst.
The reaction raw materials that catalyst of the present invention is suitable for is maleic anhydride and/or its single, ester.During charging, these raw materials dissolve in The suitable solvent, in gamma-butyrolacton and oxolane.
Catalyst of the present invention is used for the gas phase catalytic hydrogenation system 1 of maleic anhydride and/or its ester, during the 4-butanediol, the reaction temperature that is suitable for is 180-280 ℃, reaction pressure is 1-6MPa, the mol ratio of raw material acid anhydride and/or ester and solvent (as gamma-butyrolacton) is 0.1～5: 1, the mol ratio of hydrogen and acid anhydride and/or ester is 200～500: 1, and the gaseous phase volume air speed of maleate and/or ester can be up to 90 o'clock
-1
Use catalyst of the present invention to be used for maleic anhydride and/or its ester carries out vapour phase hydrogenation system 1, the 4-butanediol 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 high selectivity of 4-butanediol.In the gaseous phase volume air speed of acid anhydride and/or ester up to 90 o'clock
-1The time, the conversion ratio of acid anhydride and/or ester can reach 100%, 1, and the selectivity of 4-butanediol can reach 80 moles more than the %.Catalyst of the present invention also can be higher than at 90 o'clock in the gaseous phase volume air speed of acid anhydride and/or its ester
-1Condition under operate, at this moment certain 1, the selectivity of 4-butanediol can descend to some extent.
Following embodiment is used to illustrate in greater detail the present invention, but the present invention is not limited to this.
React among each embodiment at vapour phase hydrogenation, unstripped gas phase volume air speed all refers to convert the value under the normal temperature and pressure, maleic anhydride with MAN represent, dibutyl maleate with MDB represent, gamma-butyrolacton represents with GBL.
Embodiment 1～5th, the example of catalyst of the present invention.
Embodiment 1
With 120.78 gram Cu (NO
3)
23H
2O (Beijing Chemical Plant, chemical pure), 5.0 gram CrO
3(Beijing Chemical Plant, chemical pure), 76.1 gram 50%Mn (NO
3)
2The aqueous solution (Beijing Chemical Plant, chemical pure) and 128.5 gram Ba (OH)
2(Beijing Chemical Plant, chemical pure) and 73.2 gram Al (NO
3)
39H
2O (Beijing Chemical Plant, chemical pure) is dissolved in 1500 milliliters of decationizing water, dropping ammonia (Beijing Chemical Plant under room temperature, stirring, chemical pure), until pH6.5 ± 0.2, ageing filtration after 2 hours, washing, collecting precipitation were 120 ± 10 ℃ of dryings 10 hours, 400 ℃ of roastings 24 hours, obtain catalyst A: CuCr then
0.1Mn
0.4Ba
1.5Al
0.4O
3.8(metal is formed with the analysis of X-ray fluorescence analysis, and oxygen content is a calculated value, down together).
Embodiment 2
With 120.78 gram Cu (NO
3)
23H
2O, 25.0 gram CrO
3, 17.9 gram 50%Mn (NO
3)
2The aqueous solution, 4.30 gram Ba (OH)
2With 36.6 gram Al (NO
3)
39H
2O makes catalyst B by the mode of embodiment 1: CuCr
0.5Mn
0.1Ba
0.05Al
0.2O
2.95
Embodiment 3
Press the mode of embodiment 1, with 120.78 gram Cu (NO
3)
23H
2O, 50.0 gram CrO
3, 71.6 gram 50%Mn (NO
3)
2The aqueous solution, 17.10 gram Ba (OH)
2With 146.4 gram Al (NO
3)
39H
2O makes catalyst C:CuCrMn
0.4Ba
0.2Al
0.8O
5.8
Embodiment 4
With 96.62 gram Cu (NO
3)
23H
2O, 40.0 gram CrO
3, 71.6 gram 50%Mn (NO
3)
2The aqueous solution, 17.1 gram Ba (OH)
2With 292.80 gram Al (NO
3)
39H
2O is dissolved in 1500 milliliters of decationizing water, adds ammoniacal liquor until pH9.0 ± 0.2 under room temperature, stirring, gets slurries A, room temperature ageing 2 hours, restrains Cu (NO with 48.31 again under stirring
3)
23H
2O, 20.0 gram CrO
3, 17.91 gram 50%Mn (NO
3)
2The solution B that the aqueous solution forms in 300 milliliters of decationizing water under agitation joins among the slurries A, control pH value of solution 6.6 ± 0.2 (using ammoniacal liquor in case of necessity), stir ageing 2 hours under the room temperature, then by the mode of embodiment 1 wash, dry, roasting, make catalyst D:CuCrMn
0.5Ba
0.17Al
1.3O
6.62
Embodiment 5
With 120.78 gram Cu (NO
3)
23H
2O, 50.0 gram CrO
3, 71.6 the gram 50% Mn (NO
3)
2The aqueous solution, 17.1 gram Ba (OH)
2With 39.9 gram TiO
2(chemical reagent three factories in Tianjin produce, content 〉=99%,＜200 orders) be scattered in 1500 milliliters of decationizing water, transfer to system pH6.6 ± 0.2 with ammoniacal liquor, mode by embodiment 1 is carried out ageing, washing, drying and roasting to precipitation, obtains catalyst E:CuCrMn
0.4Ba
0.25TiO
5.65
Comparative example 1
Open embodiment 1 described method among the flat 2-233630 by the spy, with Cu (NO
3)
23H
2O, CrO
3, Mn (NO
3)
2And Ba (NO
3)
2For raw material make the comparative sample catalyst A ': CuCrMn
0.4Ba
0.2O
4.6
Table 1 is listed in the composition unification of each catalyst
Table 1
| The catalyst numbering | Form | |
| Embodiment 1 | ????A | ??CuCr 0.1Mn 0.4Ba 1.5Al 0.4O 3.8 |
| 2 | ????B | ??CuCr 0.5Mn 0.1Ba 0.05Al 0.2O 2.95 |
| 3 | ????C | ??CuCrMn 0.4Ba 0.2Al 0.8O 5.8 |
| 4 | ????D | ??CuCrMn 0.5Ba 0.17Al 1.3O 6.62 |
| 5 | ????E | ??CuCrMn 0.4Ba 0.25TiO 5.65 |
| Comparative example 1 | ????A′ | ??CuCrMn 0.4Ba 0.2O 4.6 |
Embodiment 6-13 explanation catalyst of the present invention is in maleic anhydride and/or its ester vapour phase hydrogenation system 1, the shown superior catalytic performance that goes out in the process of 4-butanediol.
Embodiment 6
Get 5 milliliters of 20～40 order catalyst A, in 10 millimeters of the internal diameters of packing into after mixing with 5 milliliters of the quartz sands of one-size, long 500 millimeters the stainless steel tubular type reactor, under 300 ℃, 2.0MPa with the hydrogen reducing catalyst of 800 ml/min flows 2 hours.Then bed temperature is reduced to 220 ℃, pressure and be adjusted to 5.0MPa, begin charging after system is stable.The material that enters is 1: 1 MAN of mol ratio and solvent GBL, and hydrogen acid anhydride mol ratio is 350: 1, and MAN gaseous phase volume air speed is 34 o'clock
-1, product adopts the PEG20000 packed column with gc analysis, detects with FID.The results are shown in Table 2.
Embodiment 7
Adopt catalyst B, reduce, react by the mode of embodiment 6, reaction temperature that different is is that 218 ℃, reaction pressure are 4.5MPa, and hydrogen acid anhydride mol ratio is 350: 1, and MAN gaseous phase volume air speed is 34 o'clock
-1, the results are shown in Table 2.
Embodiment 8
Adopt catalyst C, reduce, react by the mode of embodiment 6, reaction temperature that different is is that 234 ℃, hydrogen acid anhydride mol ratio are 225: 1, and MAN gaseous phase volume air speed is 54 o'clock
-1, the results are shown in Table 2.
Embodiment 9
Adopt catalyst D, reduce, react by the mode of embodiment 6, reaction temperature that different is is that 231 ℃, hydrogen acid anhydride mol ratio are 350: 1, and MAN gaseous phase volume air speed is 87 o'clock
-1, the results are shown in Table 2.
Embodiment 10
Adopt catalyst D, reduce, react by the mode of embodiment 6, reaction temperature that different is is that 219 ℃, hydrogen acid anhydride mol ratio are 350: 1, and MAN gaseous phase volume air speed is 54 o'clock
-1, the results are shown in Table 2.
Embodiment 11
Adopt catalyst D, mode by embodiment 6 is reduced, is reacted, and reaction temperature that different is is that 210 ℃, reaction pressure are 4.0MPa, and reaction feed is that mol ratio is 1: 1 MBD and GBL, hydrogen acid anhydride mol ratio is 350: 1, and the gaseous phase volume air speed of MDB is 54 o'clock
-1, the results are shown in Table 2.
Embodiment 12
Adopt catalyst E, reduce, react by the mode of embodiment 6, reaction temperature that different is is that 214 ℃, hydrogen acid anhydride mol ratio are 350: 1, and MAN gaseous phase volume air speed is 34 o'clock
-1, the results are shown in Table 2.
Comparative example 2
Adopt catalyst A ', reduce, react by the mode of embodiment 6, reaction temperature that different is is that 230 ℃, reaction pressure are 4.0MPa, hydrogen acid anhydride mol ratio is 400: 1, MAN gaseous phase volume air speed is 24 o'clock
-1, the results are shown in Table 2.
Table 2
| Embodiment 6 | ????7 | ????8 | ????9 | ????10 | ????11 | ????12 | Comparative example 2 | ||
| The catalyst numbering | ??A | ??B | ??C | ??D | ??D | ??D | ??E | ??A′ | |
| Reaction temperature (℃) | ??220 | ??218 | ??234 | ??231 | ??219 | ??210 | ??214 | ??230 | |
| Reaction pressure (MPa) | ??5.0 | ??4.5 | ??5.0 | ??5.0 | ??5.0 | ??4.0 | ??5.0 | ??4.0 | |
| The H2/MAN mol ratio | ??350∶1 | ??350∶1 | ??225∶1 | ??350∶1 | ??350∶1 | ??350∶1 * | ??350∶1 | ??400∶1 | |
| MAN gaseous phase volume air speed (time -1) | ??34 | ??34 | ??54 | ??87 | ??54 | ??54 * | ??34 | ??24 | |
| MAN conversion ratio (mole %) | ??100 | ??100 | ??90.8 | ?100 | ?100 | ??100 * | ??100 | ??100 | |
| Selectivity (mole %) | 1, the 4-butanediol | ??85 | ??82 | ??86 | ?88 | ?94 | ??96 | ??95 | ??50 |
| Oxolane | ??10 | ??14 | ??10 | ?8 | ?4 | ??2 | ??2 | ??40 | |
| N-butanol | ??5 | ??4 | ??4 | ?4 | ?2 | ??2 | ??3 | ??10 | |
*Numerical value system is raw material gained result with MDB herein.
Claims (10)
1. one kind is used for maleic anhydride and/or its ester vapour phase hydrogenation system 1, and the catalyst that contains Cu, Cr, Mn and Ba of 4-butanediol is characterized in that it has following general formula and forms:
CuCr
aMn
bBa
cM
dO
xWherein M is selected from Al or Ti, a=0.1～2, and b=0.05～1, c=0.05～1.5, d=0.05～1.5, x satisfies the required corresponding oxygen atomicity of each metal component valence state.
2. by the catalyst of claim 1, it is characterized in that it is by the co-precipitation and getting in the presence of alkali of the precursor of Cu, Cr, Mn, Ba, Al or Ti.
3. press the catalyst of claim 2, it is characterized in that said M is that Al and Al account for 20% when above of metal total mole number in the catalyst, catalyst makes by multiple step coprecipitation, promptly earlier precursor and 1/3～1/2 Cu, Cr, the precursor of Mn of Al, Ba formed the slurries of pH 9～10 in the presence of alkali, and then the dispersion liquid of water that adds the precursor of remaining Cu, Cr, Mn carries out co-precipitation in the presence of alkali.
4. by the catalyst of claim 2 or 3, the precursor that it is characterized in that said Cu, Cr, Mn, Ba, Al or Ti is a soluble-salt separately.
5. by the catalyst of claim 4, the precursor that it is characterized in that said Cu, Cr, Mn, Ba, Al or Ti is a nitrate separately.
6. by the catalyst of claim 2 or 3, the precursor that it is characterized in that said Cr is CrO
3
7. by the catalyst of claim 2 or 3, the precursor that it is characterized in that said Ba is Ba (OH)
2
8. by the catalyst of claim 2 or 3, the precursor that it is characterized in that said Ti is TiO
2
9. by the catalyst of claim 2 or 3, it is characterized in that said alkali is ammoniacal liquor.
10. by the catalyst of claim 2 or 3, it is characterized in that said co-precipitation pH is 6～8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95106349A CN1046434C (en) | 1995-06-14 | 1995-06-14 | Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95106349A CN1046434C (en) | 1995-06-14 | 1995-06-14 | Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1137944A true CN1137944A (en) | 1996-12-18 |
| CN1046434C CN1046434C (en) | 1999-11-17 |
Family
ID=5075886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95106349A Expired - Fee Related CN1046434C (en) | 1995-06-14 | 1995-06-14 | Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7169958B2 (en) | 2002-06-11 | 2007-01-30 | Basf Aktiengesellschaft | Method for the production of 1,4- butane-diol by combined gas-phase and liquid-phase hydrogenation |
| US7271299B2 (en) | 2002-06-11 | 2007-09-18 | Basf Aktiengesellschaft | Two-stage method for producing butanediol with intermediated separation of succinic anhydride |
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02111735A (en) * | 1988-10-20 | 1990-04-24 | New Japan Chem Co Ltd | Production of 1,4-butanediol |
| JP2596604B2 (en) * | 1988-12-14 | 1997-04-02 | 東燃株式会社 | Method for producing 1,4-butanediol and tetrahydrofuran |
| DE4326692A1 (en) * | 1993-08-10 | 1995-02-16 | Akzo Nobel Nv | Process for the production of gamma-butyrolactone |
-
1995
- 1995-06-14 CN CN95106349A patent/CN1046434C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7169958B2 (en) | 2002-06-11 | 2007-01-30 | Basf Aktiengesellschaft | Method for the production of 1,4- butane-diol by combined gas-phase and liquid-phase hydrogenation |
| US7271299B2 (en) | 2002-06-11 | 2007-09-18 | Basf Aktiengesellschaft | Two-stage method for producing butanediol with intermediated separation of succinic anhydride |
| US9168509B2 (en) | 2011-11-09 | 2015-10-27 | China Petroleum & Chemical Corp. | Hydrogenation catalysts and the preparation processes thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046434C (en) | 1999-11-17 |
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