CN101307042A - Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone - Google Patents
Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone Download PDFInfo
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000001384 succinic acid Substances 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 15
- 239000011976 maleic acid Substances 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- -1 hydrogen ester Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 claims description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 3
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 3
- 229960002097 dibutylsuccinate Drugs 0.000 claims description 3
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- RXBRCXMBFKAUAB-UHFFFAOYSA-N COC(C=C/C(=O)OC)=O.C(C=C/C(=O)OC)(=O)OC Chemical compound COC(C=C/C(=O)OC)=O.C(C=C/C(=O)OC)(=O)OC RXBRCXMBFKAUAB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing 1, 4-butanediol and co-producing tetrahydrofuran and gamma-butyrolactone. The method comprises the following steps that: maleic dialkyl ester and/or succinic acid dialkyl ester are/is used as raw material; under hydrogen existence and reaction conditions, reaction material passes through a first catalyst bed layer of CuO-AO-BO, wherein AO is Cr2O3 and/or ZnO, and BO is one or a plurality of Ba, Mg, Ti, Ce, Si, Zr and Mn oxides; then the reaction material passes through a second catalyst bed layer of CuO-MO-Al2O3, wherein MO is one or a plurality of Mn, Zn, Ba, Mg, Ti, Ce, Si and Zr oxides. Compared with the prior art, the method has the advantages that: the raw material conversion rate is more than 99 percent; the total selectivity of 1, 4-butanediol, tetrahydrofuran and gamma-butyrolactone is more than 99 percent; the catalyst stability is good.
Description
Technical field
The present invention relates to a kind of is raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, adopts gas phase hydrogenation to produce 1, the method for 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone.
Background technology
1, the 4-butyleneglycol is a kind of important basic Organic Chemicals, is mainly used in the production tetrahydrofuran (THF), polybutyl terapthalate (PBT), gamma-butyrolactone and urethane (PU).In recent years, because increasing rapidly of thermoplastic elastic fiber and elastomerics demand, in great demand as monomeric PTMEG (polytetramethylene ether diol), PTMG (PTMG), make upstream raw material 1,4-butyleneglycol demand also increases fast, each is big by 1 in the world, and 4-butyleneglycol manufacturer such as BASF, DUPON etc. are numerous and confused to be expanded and can increase production.Tetrahydrofuran (THF) is a kind of excellent solvent and important Organic Chemicals, and its maximum purposes is and 1, and the polycondensation of 4-butyleneglycol generates PTMG, and self polycondensation generates PTMEG.Gamma-butyrolactone is a kind of important Organic Chemicals and fine-chemical intermediate, also be that a kind of functional, solvability is strong, good electrical property, high boiling solvent that stability is high, nontoxic, safe in utilization, have a wide range of applications in fields such as petrochemical complex, medicine, agricultural chemicals, its maximum purposes is to produce methyl-2-pyrrolidone.
In sum, 1,4-butyleneglycol, tetrahydrofuran (THF), gamma-butyrolactone are market in urgent need, the Chemicals that added value is high, therefore, and Development and Production 1, the technology of 4-butanediol and co-producing tetrahydrofuran and gamma-butyrolactone has great importance.
1,4-butyleneglycol production method has Reppe method, Mitsubishi's den process, Kuraray method, butane one cis-butenedioic anhydride method etc.Since wherein butane one cis-butenedioic anhydride method is the eighties, along with C
4The maturation of preparing cis-butenedioic anhydride by oxidation technology grows up, and generally acknowledges that in the world this method is the operational path of Technological Economy optimum.Butane one cis-butenedioic anhydride method mainly comprises following three steps: butane direct oxidation system cis-butenedioic anhydride-cis-butenedioic anhydride esterification system dimethyl maleate-dimethyl maleate hydrogenation system 1,4-butyleneglycol.
1 of Britain DAVY company, 4-butyleneglycol production patented technology (USP4,584,419) has realized industrial application in Korea S, Japan.It adopts the explained hereafter 1 of dimethyl maleate two-stage hydrogenation, 4-butyleneglycol.First section hydrogenation under the condition of 4.5MPa, is converted into gamma-butyrolactone with dimethyl maleate at 200 ℃; Second section is at 180 ℃, 6.0MPa condition under, gamma-butyrolactone partly is converted into 1,4-butyleneglycol and tetrahydrofuran (THF), the main purpose of this technological line is to prevent 1, the double-bond hydrogenation product dimethyl succinate reaction of 4-butyleneglycol and dimethyl maleate forms polymkeric substance, causes the inactivation of catalyzer.This technology more complicated, investment is big.
After this, each company has carried out in the separate unit reactor, is that raw material carries out hydrogenation reaction production 1, the research of 4-butyleneglycol with maleic acid alkyl ester and/or succinic acid dialkyl ester.For example Chinese Fudan University has developed a kind of CuO-ZnO/ carried catalyst (CN200610026696), and the transformation efficiency of dimethyl maleate preferably reaches 100%, and the selectivity of butyleneglycol preferably reaches 75.5%.
1, in the 4-butyleneglycol production technology, be that the catalyzer of main active component is more with CuO, as the disclosed CuO-Cr of EP0143634
2O
3Catalyzer, the disclosed CuO-ZnO catalyzer of WO82/03854, the disclosed CuO-Cr of CN1182732A
2O
3-Al
2O
3Catalyzer, the disclosed CuO-MnO of CN1493569A
2-Al
2O
3Catalyzer, the disclosed CuO-Cr of EP0373947
2O
3-MnO
2Catalyzer etc.This states composition and preparation method that prior art all discloses catalyzer, and the processing condition of using these catalyzer.
At present, the method of carrying out maleic acid alkyl ester and/or succinic acid dialkyl ester hydrogenation reaction in the separate unit reaction all exists the stable bad problem of catalyzer, discover, its major cause is that succinic acid dialkyl ester reacts with the water that reaction produces, generate Succinic Acid, and Succinic Acid is had an effect attached to catalyst surface or with catalyzer consumingly, cause poisoning of catalyst or catalyzer efflorescence, cause feed stock conversion reduction or reactor beds stressor layer to fall increase at last, power consumption increases.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of production 1, the method of 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone, on the basis of simplifying technical process, can effectively solve the poisoning effect of Succinic Acid to catalyzer, catalyst stability is good, and comprehensive catalyzed reaction is effective, and the reactor beds stressor layer falls not have obviously to be increased.
The present invention produces 1, the method of 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone comprises, is raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, under hydrogen existence and reaction conditions, reaction mass is by first beds of CuO-AO-BO, and wherein AO is Cr
2O
3And/or ZnO, BO is one or more in the element oxides such as Ba, Mg, Ti, Ce, Si, Zr and Mn, and the CuO weight content is 30%～80%, and the AO weight content is 10%～70%, and the BO weight content is 0～40%; Pass through CuO-MO-Al then
2O
3Second beds, wherein MO is one or more in the element oxides such as Mn, Zn, Ba, Mg, Ti, Ce, Si and Zr, the CuO weight content is 30%～80%, the MO weight content is 10%～50%, Al
2O
3Weight content is generally 5%～40%; First beds is 1: 10～10: 1 with the catalyst volume ratio of second beds, and the ratio of optimization is 1: 5～1: 1, and optimized ratio is 1: 4～1: 2.
In the inventive method, the composition of the catalyzer that uses and preparation method all can determine by this area general knowledge in first beds and second beds, during catalyzer is formed, Cu is a main active component, other component is a structural promoter, and catalyzer can adopt conventional coprecipitation method preparation.In the first beds catalyzer, the CuO weight content is preferably 40%～70%, and the AO weight content is preferably 20%～50%, and the BO weight content is preferably 5～30%; In the second beds catalyzer, the CuO weight content is preferably 40%～70%, and the MO weight content is preferably 20%～40%, Al
2O
3Weight content is preferably 10%～30%.Owing to reasons such as preparation process and material purities, must contain a certain amount of other impurity in the catalyzer, as shaping assistant, na oxide, ferriferous oxide etc., content is generally about 2%.Catalyzer is reduced to simple substance Cu with CuO before use, to improve catalyst activity.Also can use dissimilar catalyzer in each beds, catalyzer dissimilar in each bed can use by mixed packing, also can distinguish the layering filling and use.
In the inventive method, described reaction conditions is: 160～240 ℃ of temperature of reaction, the temperature of reaction of optimizing is 180～200 ℃, reaction pressure 4.0～8.0MPa, the reaction pressure of optimizing is 5.0～6.0MPa, hydrogen ester mol ratio 100: 1～400: 1, the hydrogen ester mol ratio of optimization 200: 1～300: 1, volume space velocity 0.1～2.0h during the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
-1, volume space velocity 0.2～0.5h during the liquid of optimization
-1Concrete processing condition can specifically be selected by this area knowledge according to feedstock property and product requirement.
In the inventive method, described maleic acid alkyl ester and/or succinic acid dialkyl ester are generally the dialkyl of C1～C4, as dimethyl maleate and/or dimethyl succinate, diethyl maleate and/or diethyl succinate, dibutyl maleate and/or dibutyl succinate etc.
In the inventive method, reaction process forms the vapourous mixture that is higher than the raw material dew-point temperature for earlier the maleic acid alkyl ester of liquid and/or succinic acid dialkyl ester being vaporized in required ratio in the hot hydrogen logistics, this vapourous mixture is fed be equipped with in the reactor of hydrogenation catalyst then.
In the inventive method, described first beds and second beds can be arranged in the reactor, also can be arranged in placed in-line two reactors, preferably the former can also be provided with the bed of other type catalyst as required to simplify flow process.
The present invention produces 1 by examination maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation, the reaction mechanism of 4-butyleneglycol, tetrahydrofuran (THF), gamma-butyrolactone, poisoning of catalyst and broken major cause are that succinic acid dialkyl ester reacts with the water that reaction produces in the discovery prior art, generate Succinic Acid, and Succinic Acid is had an effect attached to catalyst surface or with catalyzer consumingly, cause poisoning of catalyst or catalyzer efflorescence, cause feed stock conversion reduction or reactor beds stressor layer to fall increase at last, power consumption increases.The inventive method efficiently solves the problems referred to above by optimizing the grating of catalyzer, and simultaneously, the catalyst system of grating has active high, the selection advantages of higher of combined reaction.The inventive method can adopt the separate unit reactor to finish maleic acid alkyl ester and/or the succinic acid dialkyl ester gas phase hydrogenation produces 1, the process of 4-butyleneglycol, tetrahydrofuran (THF), gamma-butyrolactone, solved the poisoning effect of Succinic Acid effectively to catalyzer, catalyst stability is good, the reactor beds stressor layer falls does not see increase, feed stock conversion is greater than 99%, and the product overall selectivity is greater than 99%.
Embodiment
Further specify the inventive method and effect below by embodiment.Wherein catalyzer is formed by weight, forms by ignoring impurity.
Comparative example 1
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is CuO-MnO
2/ Al
2O
3(CuO content is 65%, MnO
2Content is 15%, Al
2O
3Content is 20%), processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 1.Reaction product unit is the quality percentage composition in the table, and transformation efficiency is a molar yield, and the product overall selectivity is the mole selectivity.
Table 1CuO-MnO
2/ Al
2O
3The catalyst stability experimental result
| Time, h | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| Initially | 1.69 | 8.59 | 52.26 | 0.38 | 99.34 | 99.27 |
| 100 | 1.81 | 8.50 | 51.83 | 0.45 | 99.31 | 99.13 |
| 200 | 1.94 | 9.00 | 53.18 | 0.44 | 99.24 | 99.17 |
| 300 | 1.38 | 8.52 | 53.52 | 0.42 | 99.17 | 99.20 |
| 400 | 1.67 | 8.72 | 53.14 | 0.57 | 99.06 | 98.96 |
| 500 | 1.67 | 8.99 | 52.20 | 0.45 | 98.87 | 99.16 |
By example 1 as can be seen, feed stock conversion reduces with prolonging runtime, after estimating end, finds that catalyst strength reduces, and the part catalyzer has powder phenomenon-tion.In operation process, find that increase falls in reactor pressure.
Comparative example 2
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is CuO-Cr
2O
3(CuO content is 57%, Cr
2O
3Content is 43%), processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 2.
Table 2CuO-Cr
2O
3The evaluating catalyst result
| Time, h | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| Initially | 5.61 | 9.12 | 45.35 | 0.40 | 98.52 | 99.20 |
| 100 | 4.44 | 8.63 | 46.73 | 0.45 | 98.60 | 99.12 |
| 200 | 4.15 | 8.90 | 47.21 | 0.40 | 98.61 | 99.22 |
| 300 | 4.09 | 8.63 | 46.38 | 0.39 | 98.59 | 99.22 |
| 400 | 2.91 | 8.33 | 46.87 | 0.41 | 98.62 | 99.16 |
| 500 | 4.18 | 8.43 | 47.82 | 0.40 | 98.65 | 99.21 |
By comparative example 2 as can be seen, it is stable that feed stock conversion keeps in operation process always, but contrast table 1 and table 2 are as can be seen, CuO-Cr
2O
3The relative CuO-MnO of catalyzer initial conversion
2/ Al
2O
3Lower, and 1,4-butyleneglycol content in product liquid is relative also lower.
Embodiment 1
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is the CuO-Cr of different filling ratios
2O
3(with comparative example 2) catalyzer and CuO-MnO
2/ Al
2O
3(with comparative example 1) grading loading, processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 3.
Table 3 catalyzer grading loading test-results
| The filling ratio | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| 1∶4 | 2.29 | 8.96 | 50.58 | 0.49 | 99.29 | 99.12 |
| 1∶3 | 2.46 | 8.78 | 50.19 | 0.47 | 99.26 | 99.18 |
| 1∶2 | 2.85 | 8.29 | 50.11 | 0.46 | 99.11 | 99.19 |
| 1∶1 | 3.03 | 8.59 | 49.81 | 0.46 | 99.03 | 99.18 |
| 2∶1 | 3.19 | 8.43 | 49.48 | 0.44 | 98.75 | 99.22 |
Embodiment 2
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is 1: 3 CuO-Cr for the filling ratio
2O
3(with comparative example 2) catalyzer and CuO-MnO
2/ Al
2O
3(with comparative example 1), processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 4.
Table 4 catalyzer grading loading stability test result
| Time, h | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| Initially | 2.46 | 8.96 | 50.19 | 0.47 | 99.26 | 99.18 |
| 100 | 2.92 | 8.78 | 51.19 | 0.52 | 99.28 | 99.05 |
| 200 | 2.13 | 8.69 | 49.41 | 0.51 | 99.41 | 99.07 |
| 300 | 2.19 | 9.43 | 49.48 | 0.46 | 99.43 | 99.12 |
| 400 | 2.44 | 8.63 | 48.73 | 0.45 | 99.40 | 99.11 |
| 500 | 2.15 | 8.90 | 49.11 | 0.40 | 99.38 | 99.21 |
By embodiment 2 as can be seen, by the grading loading of catalyzer, catalyst stability is good, and feed stock conversion is greater than 99%, and the product overall selectivity is greater than 99%, and reactor pressure decrease does not increase.
By comparative example 1～2 as can be seen, CuO-Cr
2O
3The good stability of catalyzer, CuO-MnO
2/ Al
2O
3The initial activity of catalyzer is good.By embodiment 1～2 as can be seen, both gratings are used, both can have been brought into play CuO-Cr according to the inventive method
2O
3The advantage of good stability has been brought into play CuO-MnO again
2/ Al
2O
3Catalyzer initial conversion height, 1, the advantage that 4-butyleneglycol output is high improves the whole synthesis reaction effect greatly.
Embodiment 3～6
According to the inventive method, use different catalyzer, cooperate appropriate processing condition, be that raw material carries out hydrogenation reaction with the dimethyl maleate, actual conditions and reaction result see Table 4, table 5 and table 6.If use dissimilar catalyzer in each beds, catalyzer is by the filling of equal volume mixed.Wherein embodiment 6 uses dibutyl maleate and 1: 1 mixture of dibutyl succinate volume ratio to be raw material.
Table 4 embodiment 3～6 catalyzer
Table 5 embodiment 3～6 operational conditions
| Embodiment | Temperature, ℃ | Pressure, MPa | Air speed, h -1 | Hydrogen/ester ratio |
| 3 | 190 | 6.0 | 0.25 | 200∶1 |
| 4 | 200 | 5.0 | 0.30 | 300∶1 |
| 5 | 195 | 6.0 | 0.40 | 200∶1 |
| 6 | 190 | 6.0 | 0.25 | 200∶1 |
Table 6 embodiment 3～6 reaction results
Claims (10)
1, a kind of production 1, the method of 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone, with maleic acid alkyl ester and/or succinic acid dialkyl ester is raw material, it is characterized in that: under hydrogen existence and reaction conditions, reaction mass is by first beds of CuO-AO-BO, and wherein AO is Cr
2O
3And/or ZnO, BO is one or more in Ba, Mg, Ti, Ce, Si, Zr and the Mn element oxide, and the CuO weight content is 30%～80%, and the AO weight content is 10%～70%, and the BO weight content is 0～40%; Pass through CuO-MO-Al then
2O
3Second beds, wherein MO is one or more in Mn, Zn, Ba, Mg, Ti, Ce, Si and the Zr element oxide, the CuO weight content is 30%～80%, the MO weight content is 10%～50%, Al
2O
3Weight content is 5%～40%; First beds is 1: 10～10: 1 with the catalyst volume ratio of second beds.
2, in accordance with the method for claim 1, it is characterized in that the CuO weight content is 40%～70% in the described first beds catalyzer, the AO weight content is 20%～50%, and the BO weight content is 5～30%; In the second beds catalyzer, the CuO weight content is 40%～70%, and the MO weight content is 20%～40%, Al
2O
3Weight content is 10%～30%.
3,, it is characterized in that described first beds and the catalyst volume ratio of second beds are 1: 5～1: 1 according to claim 1 or 2 described methods.
4,, it is characterized in that described first beds and the catalyst volume ratio of second beds are 1: 4～1: 2 according to claim 1 or 2 described methods.
5, according to claim 1 or 2 described methods, it is characterized in that described reaction conditions is: 160～240 ℃ of temperature of reaction, reaction pressure 4.0～8.0MPa, volume space velocity 0.1～2.0h when hydrogen ester mol ratio 100: 1～400: 1, the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
-1
6, according to claim 1 or 2 described methods, it is characterized in that described reaction conditions is: 180～200 ℃ of temperature of reaction, reaction pressure 5.0～6.0MPa, volume space velocity 0.2～0.5h when hydrogen ester mol ratio 200: 1～300: 1, the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
-1
7,, it is characterized in that described maleic acid alkyl ester and/or succinic acid dialkyl ester are the dialkyl of C1～C4 according to claim 1 or 2 described methods.
8,, it is characterized in that described maleic acid alkyl ester and/or succinic acid dialkyl ester are dimethyl maleate and/or dimethyl succinate, diethyl maleate and/or diethyl succinate or dibutyl maleate and/or dibutyl succinate according to claim 1 or 2 described methods.
9, according to claim 1 or 2 described methods, it is characterized in that reaction process is the maleic acid alkyl ester of liquid and/or succinic acid dialkyl ester to be vaporized in required ratio to form the vapourous mixture that is higher than the raw material dew-point temperature earlier, feeds this vapourous mixture then and is equipped with in the reactor of hydrogenation catalyst in the hot hydrogen logistics.
10,, it is characterized in that described first beds and second beds are arranged in the reactor, or be arranged in placed in-line two reactors according to claim 1 or 2 described methods.
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