CN102190582B - Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol - Google Patents
Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol Download PDFInfo
- Publication number
- CN102190582B CN102190582B CN201010129552.4A CN201010129552A CN102190582B CN 102190582 B CN102190582 B CN 102190582B CN 201010129552 A CN201010129552 A CN 201010129552A CN 102190582 B CN102190582 B CN 102190582B
- Authority
- CN
- China
- Prior art keywords
- dimethyl succinate
- pressure
- hydrogen
- bdo
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method of simultaneously producing dimethyl succinate (DMS) and 1, 4-butyl glycol. The method can also be used to simultaneously produce at least one of Tetrahydro furan (THF) and gamma-irradiation butyl lactone (GBL). In the invention, dimethyl maleate (DMM) is used as raw materials and contacts with hydrogen under the condition of gas phase in a low pressure reaction district and a middle pressure reaction district respectively. A low-pressure reactor and a middle-pressure reactor are equipped with a catalyst. DMS products are produced in the low pressure reaction district and 1, 4-butyl glycol products are produced in the middle pressure reaction district. Simultaneously, at least one of the GBL and THF can be produced in the middle pressure reaction district. Purity of DMS can reach over 99.5% without refining through using a gas-liquid separator. In the invention, the method is used in mild condition; heavier component does not need to be circulated; operation is simple; transesterification type polymerization and other side reactions are greatly reduced in a system.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of method of simultaneously producing dimethyl succinate and BDO.
Background technology
Dimethyl succinate (DMS) is mainly used in synthetic perfume and foodstuff additive, it is also a kind of important chemical intermediate simultaneously, be widely used in producing of multi-chemical, as further hydrogenation produces 1,4-butyleneglycol, gamma-butyrolactone (GBL), tetrahydrofuran (THF) (THF) etc., or the Biodegradable material poly butylene succinate (PBS) having a extensive future with the production application of BDO ester interchange polymerization.
Dimethyl succinate is mainly taking succinic acid and methyl alcohol as raw material at present, under the katalysis of concentrated sulfuric acid catalyst, obtains by esterification.The technique side reaction of this employing sulphuric acid catalysis esterification is many, and yield is low, aftertreatment complexity, and equipment corrosion is serious, and the methyl-sulfate of by-product is violent in toxicity, serious environment pollution.
A kind of open method that dimethyl succinate is prepared in continuous hydrogenation reaction of carrying out under liquid-phase condition taking dimethyl maleate (DMM) as raw material in US Patent No. 5872276A, the method adopts fixed-bed tube reactor, wherein dimethyl maleate and hydrogen counter current contact in reaction tubes, reaction pressure is 100～300 bar, temperature of reaction is 40～100 DEG C, and liquid hourly space velocity is 0.6～1.5g DMM/ml Cat.h
-1.The required reaction pressure of this liquid-phase hydrogenatin is higher, makes facility investment and process cost all higher.
1,4-butyleneglycol is a kind of important organic and fine chemical material, mainly for the production of polybutylene terephthalate (PBT), urethane (PU), gamma-butyrolactone (GBL), N-Methyl pyrrolidone (NMP), tetrahydrofuran (THF) (THF) etc., especially its derivative fine chemical product of high added value especially.
In the industrial production of BDO, a kind of compared with the maleic acid ester hydrogenation route for the exploitation of Dai Wei company of the tool market competitiveness and development potentiality, described in patent CN1028093C at present.The method taking toxilic acid alkyl ester particularly dimethyl maleate or ethyl maleate as raw material, under hydrogenation catalyst effect, carry out hydrogenation reaction, generate BDO, and can by-product tetrahydrofuran (THF) and/or gamma-butyrolactone, classical technique as shown in Figure 1.Toxilic acid alkyl ester enters preheater with together with circulating hydrogen from recycle compressor as dimethyl maleate, dimethyl maleate is vaporized under the stripping effect of hydrogen, flow to into hydrogenator from preheater mixed steam out, under catalyst action, generate 1, 4-butyleneglycol, tetrahydrofuran (THF) and/or gamma-butyrolactone, reaction product enters gas-liquid separator after cooling, isolated gas (overwhelming majority is hydrogen) is mixed into preheater with supplementary fresh hydrogen, liquid enters separation and purification unit, after refining, obtain 1, 4-butyleneglycol, tetrahydrofuran (THF) and/or gamma-butyrolactone product.
US4656297A described a kind of by dimethyl succinate Hydrogenation the method for tetrahydrofuran (THF) and BDO.In the method, taking dimethyl succinate as raw material, under Cu-Cr catalyst effect, carry out hydrogenation reaction, reaction pressure is 7～17.5Mpa, when temperature of reaction is that in 170～220 DEG C of situations, reaction product is mainly 1,4-butyleneglycol, when temperature of reaction is that in 220～248 DEG C of situations, reaction product is mainly tetrahydrofuran (THF).The method reaction pressure is higher, can cause facility investment and process cost higher.In addition, in order to reduce the generation of transesterification reaction, in dimethyl succinate logistics, need to add methanol solvate.
Patent CN200480035623.7 discloses a kind of method that hydrogenation of diester with unsaturated dicarboxylic acid and/or acid anhydride is prepared tetrahydrofuran (THF).In the method, first the diester of unsaturated dicarboxylic acid and/or acid anhydride is converted into dimethyl succinate with hydrogen part under catalyst action in pre-reaction zone, and this step reaction can be carried out under liquid phase, also can under gas phase, carry out; Then, the diester that contains dimethyl succinate, unconverted unsaturated dicarboxylic acid and/or acid anhydride, the mixing steam of hydrogen stream enter in main reactor jointly, under another kind of catalyst action, react, and generate cyclic ethers tetrahydrofuran (THF) and by product BDO.Wherein, in the time being gas phase hydrogenation in pre-reaction zone, will cause several problems: the one, pre-reactor is identical with reaction pressure in main reactor, is 30～70 higher bar, and the process cost of the pre-reaction zone that this sample can move under lower pressure increases; The 2nd, two kinds of catalyzer in pre-reaction zone and main reaction region, at least one catalyzer is not preferably moving under reaction conditions, indirectly causes cost to increase; In addition, with hydrogen ester in reaction zone and main reaction region than identical, and reaction needed in main reaction region is carried out under than (being preferably 258 left and right) at higher hydrogen ester, internal recycle amounts of hydrogen in pre-reaction zone, far above theoretical aequum, causes operation energy consumption to increase like this.
Summary of the invention
The object of this invention is to provide a kind of under gentle reaction conditions, produce dimethyl succinate and 1 simultaneously, the method of 4-butyleneglycol, the method also can be prepared tetrahydrofuran (THF) and gamma-butyrolactone simultaneously, can be according to the output of the flexible modulation dimethyl succinate of market demand and BDO and tetrahydrofuran (THF), gamma-butyrolactone product.
For solving above technical problem, the technical solution used in the present invention is:
A method of simultaneously producing dimethyl succinate and BDO, comprises the following steps:
1) raw material dimethyl maleate is mixed in low pressure preheater (LPP with hydrogen, dimethyl maleate is vaporized under the stripping effect of hydrogen, obtain mixing steam;
2) make the mixing steam described in step 1 that catalytic hydrogenation reaction occur in low-pressure reactor, and make described dimethyl maleate all change into dimethyl succinate;
3) by laggard the product condensation of catalytic hydrogenation reaction described in step 2 row gas-liquid separation, a part for separating obtained liquid is as dimethyl succinate product, and another part enters Zhong Ya reaction zone, downstream;
4) dimethyl succinate that enters middle pressure reaction zone described in step 3 is mixed in middle pressure preheater with hydrogen, dimethyl succinate is vaporized under the stripping effect of hydrogen, enter again in middle-pressure reactor catalytic hydrogenation reaction occurs, generate BDO;
5) by laggard the product condensation of catalytic hydrogenation reaction described in step 4 row gas-liquid separation, separating obtained liquid enters separation and purification district, isolates BDO.
Aforesaid method, taking dimethyl maleate as raw material, contacts with hydrogen respectively in He Zhongya reaction zone, low pressure reaction district under gas phase condition, produces dimethyl succinate product in low pressure reaction district, in middle pressure reaction zone, produces BDO product.The ratio of dimethyl succinate product and BDO product can be according to market demand flexible, and the two mass ratio can change between 1: 99 to 99: 1.
In step 1, for ensureing that most dimethyl maleate is vaporized, hydrogen in described low pressure preheater (LPP is excessive is necessary, and the mol ratio of described hydrogen and dimethyl maleate is 30: 1～200: 1, is preferably 50: 1～120: 1.
In step 2, the dimethyl maleate hydrogenation reaction occurring in described low-pressure reactor, for double-bond hydrogenation reaction fast, can be carried out under relatively mild reaction conditions; Described low-pressure reactor is adiabatic tubular reactor, and its ingress temperature is 100～200 DEG C, preferably 120～160 DEG C; Reaction pressure is 0.5～3.0MPa, preferably 1.0～2.0MPa; The liquid hourly space velocity of described dimethyl maleate is 0.5～5.0h
-1, preferably 1.0～3.0h
-1.
In step 2, described catalytic hydrogenation reaction catalyzer used can be palladium catalyst, and described palladium catalyst is load type palladium catalyst, and its carrier is selected from one or more the mixture in oxide compound or the carbon etc. of oxide compound, silicon of aluminium.Preferably, described catalytic hydrogenation reaction used catalyst is copper-zinc oxide catalyst.
Preferably, described copper-zinc oxide catalyzer is Cu/ZnO/Al
2o
3three-way catalyst, is made up of active ingredient copper, zinc oxide and aluminum oxide, and the mass percent of each component is: copper 45.5～46.5%, zinc oxide 44.5～49.5%, aluminum oxide 5.5～9.5%.
Described Cu/ZnO/Al
2o
3the preparation method of three-way catalyst comprises the steps:
1) co-precipitation: the soluble salt of copper, zinc, aluminium is mixed in proportion, dissolving is made into the metal ion solution that metal ion total concn is 0.6～1.2M, then the precipitant solution that is under agitation 0.5～1.6M by metal ion solution and concentration is carried out co-precipitation, and in coprecipitation process, solution temperature is 50～90 DEG C; PH is 6.5～8.0.Preferably, described metal ion solution is the solution of nitrate, acetate or other soluble salt of copper, zinc, aluminium, but can not contain Cl, S ion; Described precipitation agent is sodium hydroxide, sodium carbonate, ammoniacal liquor; The solvent of described metal ion solution and precipitant solution is water.
2) ageing: after co-precipitation finishes, this precipitation solution is stirred under the constant temperature of 50～90 DEG C and carry out for 1～45 hour obtaining precursor precipitation after ageing.Preferably, carry out promoting ageing process by stirring precipitation solution.
3) washing: washing presoma precipitation, remove foreign ion.
4) dry and roasting: by the precursor precipitation after washing, be warming up to roasting under constant temperature after maturing temperature after oven dry.
Described step 1) in.Preferably, described bake out temperature is 95～120 DEG C; Maturing temperature is 350～550 DEG C, and roasting time is 3～6 hours.
The Cu/ZnO/Al that the present invention uses in the reaction for dimethyl succinate at the dimethyl maleate Hydrogenation in low pressure reaction district
2o
3three-way catalyst, the copper-based catalysts of preparing than traditional method has more regular pore distribution and larger specific surface area, and this catalyzer shows good hydrogenation activity and selectivity after reduction activation in dimethyl maleate reaction, and target product has single-minded selectivity and good thermostability.Meanwhile, owing to having used Cu, Zn, the Al catalyzer of specific composition, with specific reaction conditions combination, dimethyl maleate can almost be transformed completely under higher raw material air speed, and obtaining higher dimethyl succinate selectivity, by product is few, easily separated.
At above-mentioned Cu/ZnO/Al
2o
3under three-way catalyst katalysis and under above-mentioned optimum condition, there is hydrogenation reaction in dimethyl maleate in low-pressure reactor, and its transformation efficiency can reach 100%, and mole selectivity of dimethyl succinate can reach more than 99.5%.Due to the dimethyl succinate purity higher (being greater than 99.5%) of gained, do not need to carry out further separation and purification and can be used as product, for raw material or the other field of senior solvent, poly-succinic dimethyl ester.
In step 4, described middle-pressure reactor is adiabatic tubular reactor, and the temperature of its ingress is 140～220 DEG C, preferably 160～190 DEG C; Reaction pressure is 4.0～8.0MPa, preferably 5.0～7.0MPa; The mol ratio of described hydrogen and dimethyl succinate is 100～400, preferably 150～300; The liquid hourly space velocity of described dimethyl succinate is less than the liquid hourly space velocity of dimethyl maleate in low-pressure reactor, is preferably 1/10～2/3 of described dimethyl maleate liquid hourly space velocity, most preferably is 1/5～1/2 of described dimethyl maleate liquid hourly space velocity.
In step 4, described catalytic hydrogenation reaction used catalyst is copper-zinc oxide catalyst, and this catalyzer must pass through reducing gas reduction activation before use.Especially, the catalyzer of employing is the copper/zinc described in patent 200610026696.0/carrier three-way catalyst.
Dimethyl succinate in middle-pressure reactor under the katalysis of catalyzer with hydrogen reaction, generate major part be the product of BDO, in this product, may also contain at least one in a small amount of tetrahydrofuran (THF) and gamma-butyrolactone; Wherein, the weight percent that the total amount of tetrahydrofuran (THF), gamma-butyrolactone or tetrahydrofuran (THF) and gamma-butyrolactone accounts for gross product can be as required regulate by changing reaction conditions.
In step 5, from middle-pressure reactor reaction product out, after gas-liquid separation, product liquid enters separation and purification district, obtains BDO product at this, or obtains respectively BDO product and a small amount of tetrahydrofuran (THF) product and gamma-butyrolactone product.
Can also isolate a small amount of heavy constituent in separation and purification district, described heavy constituent is as by product beta-hydroxymethyl butyrate of the dimethyl succinate of the not complete reaction of minute quantity and minute quantity etc., and the mass percent that these heavy constituents account for the gross product of catalytic hydrogenation reaction described in step 4 is less than 1.0%.If these heavy constituents are recycled to low-pressure reactor or the middle-pressure reactor of upstream, very easily there is transesterification reaction, the oligopolymer generating causes disadvantageous effect to activity and the life-span etc. of the catalyzer in reactor, these heavy constituents will not be recycled to low-pressure reactor or the middle-pressure reactor of upstream for this reason, carry out harmless treatment and utilization but enter heavy constituent treatment system.Like this, not only greatly avoided because of the heavy constituent generation of the ester interchange polymerization thing causing that circulates, and reduced facility investment and extended catalyst life.
Preferably, in aforesaid method of the present invention: the gained of gas-liquid separation described in step 3 gas is hydrogen, this hydrogen can be delivered to the low pressure preheater (LPP described in step 1 by low pressure recycle compressor, now, the hydrogen described in step 1 is the mixing from the hydrogen of low pressure recycle compressor and supplementary fresh hydrogen; Equally, the gas (hydrogen) of the gained of gas-liquid separation described in step 5 can be delivered to the middle pressure preheater described in step 4 by Medium pressure cycle compressor, now, the hydrogen described in step 4 is the mixing from the hydrogen of Medium pressure cycle compressor and supplementary fresh hydrogen.
In aforesaid method of the present invention, the pressure difference of the catalytic hydrogenation reaction of Yu Zhongya reaction zone, low pressure reaction district, the pressure in low pressure reaction district is 0.5～3.0MPa, preferably 1.0～2.0MPa; The pressure in middle-pressure reactor district is 4.0～8.0MPa, preferably 5.0～7.0MPa.Because producing in low pressure reaction district of dimethyl succinate carried out, thereby than more having saved process cost under high pressure.
Compared with prior art, advantage of the present invention is:
1) defect and the deficiency of patent US5872276A, US4656297A have been overcome, compared with patent CN200480035623.7, can produce dimethyl succinate and 1 simultaneously, 4-butyleneglycol and/or tetrahydrofuran (THF), gamma-butyrolactone, and can under the condition of milder, produce more neatly dimethyl succinate product;
2) produce dimethyl succinate product and 1 taking dimethyl maleate as raw material simultaneously, 4-butyleneglycol product, and can regulate dimethyl succinate product and 1 according to market demand, the amount of 4-butyleneglycol product, the dimethyl succinate and 1 of simultaneously producing, 4-butyleneglycol can carry out ester interchange polymerization and produce Biodegradable material poly butylene succinate (PBS), has a extensive future;
3) Yu Zhongya reaction zone, low pressure reaction district is relatively independent, very little on the impact of another reaction zone while regulating the processing condition of a certain reaction zone, and whole system operation is simpler and easy and flexible;
4) dimethyl succinate can reach more than 99.5% without refining purity after gas-liquid separator separates, and technique is simple, mild condition, and energy consumption is low, less investment;
5) heavy constituent does not need circulation, operates more simply, and has greatly reduced the generation of ester interchange polymerization and other side reaction.
Brief description of the drawings
Fig. 1 is the typical process flow schematic diagram of prior art;
Fig. 2 is the process flow diagram of the inventive method.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that following embodiment is only not used in and limits the scope of the invention for the present invention is described.In addition, should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Process flow diagram (the miscellaneous equipment needing in industrial production as shown in Figure 2, as pump, interchanger, compressor, recycle compressor, safety valve, control valve, storage tank etc., also unlisted in the accompanying drawings, these utility appliance can be according to interpolations such as chemical engineering equipment requirements).The raw material dimethyl maleate (DMM) of 115.2kg/h 1 enters low pressure preheater (LPP 2 by the road, from the circulating hydrogen of low pressure recycle compressor by the road 7 with converge from the fresh hydrogen of pipeline 8, then 9 also enter low pressure preheater (LPP 2 by the road, dimethyl maleate is vaporized under the stripping effect of hydrogen, in mixing steam, the mol ratio of hydrogen and dimethyl maleate is 80: 1, this mixing steam logistics 3 enters low-pressure reactor 4 by the road, in low-pressure reactor 4, catalyzer is housed, at 140 DEG C, under 1.0MPa condition, dimethyl maleate is dimethyl succinate (DMS) by whole hydrogenation.Cooled mixture flow 5 enters low-pressure gas-liquid separator 6 by the road, entering low pressure preheater (LPP at this isolated hydrogen through recycle compressor recycles, the about 29.2kg/h via line 11 of isolated a part of dimethyl succinate is extracted out as product, its purity is 99.8% (with gas chromatographic analysis), and the dimethyl succinate of the about 87.6kg/h of another part enters middle pressure reaction zone.
The dimethyl succinate of via line 10 enters middle pressure preheater 12, from the hydrogen of Medium pressure cycle compressor by the road 17 with converge from the fresh hydrogen of pipeline 18, then 19 also enter after mixing with dimethyl succinate in middle pressure preheater 12 and enter middle-pressure reactor 14 by the road, cupric oxide/zinc oxide/carrier cylindrical pellet (φ 3mm × 3mm) catalyzer is housed in middle-pressure reactor 14, its preparation process is as described in patent CN200610026696.0 embodiment 3, its loadings is about 183L, at 175 DEG C, under 6.0MPa condition, dimethyl succinate and hydrogen reaction, generation comprises 1, 4-butyleneglycol (BDO), the mix products of tetrahydrofuran (THF) (THF) and γ-Ding Nei (GBL) ester, after this mixture is cooling, enter MP (medium pressure) separator 16 through circuit 15, enter Medium pressure cycle compressor at this isolated hydrogen, after converging with fresh hydrogen, enter middle pressure preheater 12 through circuit 19, liquid mixture via line 20 enters separation and purification district 21.In separation and purification district, almost pure tetrahydrofuran (THF), gamma-butyrolactone and BDO are separated respectively, and via line 22,23,24 extraction respectively, the about 48.4kg/h of BDO product, the about 1.3kg/h of tetrahydrofuran (THF) product, the about 3.3kg/h of gamma-butyrolactone product.
In the present embodiment, the catalyzer of low-pressure reactor 4 interior fillings is Cu/ZnO/Al
2o
3three-way catalyst, the preparation process of this catalyzer is: the deionized water that the nitrate of three kinds of metals is dissolved in about 1000L by the ratio that is 1: 0.75: 0.25 in the mol ratio of Cu, Zn, Al is made into metal ion solution, about 192kg Na
2cO
3be dissolved in 1160L water and be precipitated agent solution.In the reactor stirring at a band, controlling solution temperature in still is 60 DEG C of left and right, under agitation metal ion solution is joined in precipitant solution and carries out precipitin reaction with certain flow rate, and controlling precipitation terminal pH is 7.0.After having precipitated at 60 DEG C precipitation 1h.Afterwards after filtration, washing is removed hetero-ion, dry 12h at 120 DEG C, roasting 4h in 450 DEG C of air atmospheres.The loadings of this catalyzer is about 75kg, and its bulk density is 1.5kg/L, and specific surface area is 101m
2/ g, mean pore size is 18.4nm.This catalyzer before for hydrogenation reaction at 200 DEG C with H
2contact 10h activates.
Technical process is identical with embodiment 1, difference is dimethyl maleate inlet amount, low pressure reaction district hydrogen ester ratio and middle pressure temperature of reaction, correspondingly, the produced quantity of each product is also different, wherein, the purity of the dimethyl succinate product of extraction is 99.75% (with gas chromatographic analysis), specifically as shown in table 1.
In the present embodiment, the catalyzer of low-pressure reactor 4 interior fillings is Cu/ZnO/Al
2o
3three-way catalyst, as shown in Example 1, difference is that the mol ratio of Cu, Zn, Al is 1: 0.85: 0.25 for the preparation process of this catalyzer and reactivation process.The loadings of this catalyzer is about 76kg, and catalyst bulk density is about 1.52kg/L, and specific surface area is 89m
2/ g, mean pore size is 19.3nm.
Technical process is identical with embodiment 1, difference is dimethyl maleate inlet amount, low pressure reaction district hydrogen ester ratio, temperature of reaction and pressure, and hydrogen ester ratio, the temperature and pressure of middle pressure reaction zone, correspondingly, the produced quantity of each product is also different, wherein, the purity of the dimethyl succinate product of extraction is 99.5% (with gas chromatographic analysis), specifically as shown in table 1.
In the present embodiment, the catalyzer of low-pressure reactor 4 interior fillings is Cu/ZnO/Al
2o
3three-way catalyst, as shown in Example 1, difference is that the mol ratio of Cu, Zn, Al is 1: 0.80: 0.25 for the preparation process of this catalyzer and reactivation process.The loadings of this catalyzer is about 74kg, and catalyst bulk density is about 1.48kg/L, and specific surface area is 100m
2/ g, mean pore size is 20nm.
Technical process is identical with embodiment 1, difference is dimethyl maleate inlet amount, low pressure reaction district hydrogen ester ratio, temperature of reaction and pressure, and hydrogen ester ratio, the temperature and pressure of middle pressure reaction zone, correspondingly, the produced quantity of each product is also different, wherein, the purity of the dimethyl succinate product of extraction is 99.5% (with gas chromatographic analysis), specifically as shown in table 1.
In the present embodiment, identical catalyzer in the interior filling of low-pressure reactor 4 and embodiment 3, difference is that loadings is about 100kg.
Technical process is identical with embodiment 1, difference is dimethyl maleate inlet amount, low pressure reaction district hydrogen ester ratio, temperature of reaction and pressure, and hydrogen ester ratio, the temperature and pressure of middle pressure reaction zone, correspondingly, the produced quantity of each product is also different, wherein, the purity of the dimethyl succinate product of embodiment 5 and embodiment 6 extraction is respectively 99.6%, 99.4 (with gas chromatographic analysis), specifically as shown in table 1.
In embodiment 5 and embodiment 6, identical catalyzer in the interior filling respectively of low-pressure reactor 4 and embodiment 1 and embodiment 2.
Comparative example
Process flow diagram as shown in Figure 1.Together with the dimethyl maleate of 115.2kg/h and circulating hydrogen from recycle compressor and supplementary fresh hydrogen, enter preheater 1, dimethyl maleate is vaporized under the stripping effect of hydrogen, flow to into hydrogenator 2 from preheater mixed steam out, in hydrogenator 2, be equipped with embodiment 1 in identical catalyzer in middle-pressure reactor, at 175 DEG C, under 6.0MPa condition, under dimethyl maleate and hydrogen catalyst action, generate 1, 4-butyleneglycol, tetrahydrofuran (THF), the mix products of gamma-butyrolactone, reaction product enters gas-liquid separator 3 after cooling, isolated gas (overwhelming majority is hydrogen) is mixed into preheater with supplementary fresh hydrogen, liquid enters separation and purification unit 4, after refining, obtain 1, 4-butyleneglycol, tetrahydrofuran (THF) and gamma-butyrolactone product, its output is respectively 60.48kg/h, 3.45kg/h, 5.50kg/h, a small amount of dimethyl maleate, dimethyl succinate and other heavy constituents are circulated to preheater 1.
Claims (9)
1. a method of simultaneously producing dimethyl succinate and BDO, comprises the following steps:
1) raw material dimethyl maleate is mixed in low pressure preheater (LPP with hydrogen, dimethyl maleate is vaporized under the stripping effect of hydrogen, obtain mixing steam;
2) make the mixing steam described in step 1 that catalytic hydrogenation reaction occur in low-pressure reactor, and make described dimethyl maleate all change into dimethyl succinate; In low-pressure reactor, the pressure of catalytic hydrogenation reaction is 0.5～3.0Mpa;
3) by laggard the product condensation of catalytic hydrogenation reaction described in step 2 row gas-liquid separation, a part for separating obtained liquid is as dimethyl succinate product, and another part enters Zhong Ya reaction zone, downstream;
4) dimethyl succinate that enters middle pressure reaction zone described in step 3 is mixed in middle pressure preheater with hydrogen, dimethyl succinate is vaporized under the stripping effect of hydrogen, enter again in middle-pressure reactor catalytic hydrogenation reaction occurs, generate BDO; In middle-pressure reactor, the pressure of catalytic hydrogenation reaction is 4.0～8.0Mpa;
5) by laggard the product condensation of catalytic hydrogenation reaction described in step 4 row gas-liquid separation, separating obtained liquid enters separation and purification district, isolates BDO;
In step 2, described catalytic hydrogenation reaction catalyzer used is made up of active ingredient copper, zinc oxide and aluminum oxide, and the mass percent of each component is: copper 45.5～46.5%, zinc oxide 44.5～49.5%, aluminum oxide 5.5～9.5%;
In described low-pressure reactor, the liquid hourly space velocity of dimethyl maleate is 1.0～3.0h-1; In described middle-pressure reactor the liquid hourly space velocity of dimethyl succinate be dimethyl maleate in low-pressure reactor liquid hourly space velocity 1/10～2/3;
The gained of gas-liquid separation described in step 3 gas is hydrogen, and this hydrogen is delivered to the low pressure preheater (LPP described in step 1 by low pressure recycle compressor; The gas of the gained of gas-liquid separation described in step 5 is delivered to the middle pressure preheater described in step 4 by Medium pressure cycle compressor.
2. a kind of method of simultaneously producing dimethyl succinate and BDO as claimed in claim 1, is characterized in that, the purity of the dimethyl succinate product described in step 3 is greater than 99.5%, does not need further refining.
3. a kind of method of simultaneously producing dimethyl succinate and BDO as claimed in claim 1, is characterized in that, in step 1, the mol ratio of described hydrogen and dimethyl maleate is 30:1～200:1.
4. a kind of method of simultaneously producing dimethyl succinate and BDO as claimed in claim 1, is characterized in that, in step 2, the temperature in of described low-pressure reactor is 100～200 DEG C, and the pressure of described catalytic hydrogenation reaction is 0.5～3.0Mpa.
5. one as claimed in claim 1 is produced dimethyl succinate and 1 simultaneously, the method of 4-butyleneglycol, it is characterized in that, in step 4, the mol ratio of described hydrogen and dimethyl succinate is 100:1～400:1, the temperature in of described middle-pressure reactor is 140～220 DEG C, and the pressure of described catalytic hydrogenation reaction is 4.0～8.0Mpa.
6. a kind of method of simultaneously producing dimethyl succinate and BDO as claimed in claim 1, is characterized in that, in step 4, also contains at least one in tetrahydrofuran (THF) and gamma-butyrolactone in the product of described catalytic hydrogenation reaction.
7. a kind of method of simultaneously producing dimethyl succinate and BDO as claimed in claim 6, is characterized in that, in step 5, obtains respectively BDO, tetrahydrofuran (THF) and gamma-butyrolactone product in described separation and purification district.
8. the one as described in arbitrary claim in claim 1-7 is produced dimethyl succinate and 1 simultaneously, the method of 4-butyleneglycol, it is characterized in that, in step 5, can also separate and obtain heavy constituent in described separation and purification district, the mass percent that described heavy constituent accounts for the gross product of catalytic hydrogenation reaction described in step 4 is less than 1%.
9. a kind of method of simultaneously producing dimethyl succinate and BDO as claimed in claim 8, is characterized in that, described heavy constituent directly enters heavy constituent treatment system and carries out harmless treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010129552.4A CN102190582B (en) | 2010-03-19 | 2010-03-19 | Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010129552.4A CN102190582B (en) | 2010-03-19 | 2010-03-19 | Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102190582A CN102190582A (en) | 2011-09-21 |
| CN102190582B true CN102190582B (en) | 2014-06-18 |
Family
ID=44599546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010129552.4A Active CN102190582B (en) | 2010-03-19 | 2010-03-19 | Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190582B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101632483B1 (en) * | 2014-04-11 | 2016-06-22 | 씨제이제일제당 (주) | Process for treating homoserin compounds |
| CN110357782B (en) * | 2018-04-11 | 2022-03-01 | 中国科学技术大学 | Preparation method of medium-long chain fatty alcohol and ester thereof |
| CN111018669B (en) * | 2018-10-09 | 2022-10-04 | 中国石油化工股份有限公司 | Continuous preparation method of 1, 4-butanediol |
| CN114539070B (en) * | 2020-11-24 | 2023-03-03 | 中国科学院大连化学物理研究所 | Method for preparing 1,4-butanediamine from 1, 4-butanedioic acid |
| WO2022190141A1 (en) | 2021-03-12 | 2022-09-15 | Conser S.P.A. | Process for the co-production of dialkyl succinate and 1,4-butanediol by hydrogenating dialkyl maleate in two stages. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1857771A (en) * | 2006-05-18 | 2006-11-08 | 复旦大学 | High selectivity catalyst for preparing tetrahydrofuran and its preparing process |
| CN101307042A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19506096A1 (en) * | 1995-02-22 | 1996-08-29 | Bayer Ag | Process for the preparation of succinic acid dialkyl esters |
| GB0329152D0 (en) * | 2003-12-16 | 2004-01-21 | Davy Process Techn Ltd | Process |
| CN1850328A (en) * | 2006-05-18 | 2006-10-25 | 复旦大学 | High-selectivity catalyst for preparing 1,4-butanediol and its preparing method |
-
2010
- 2010-03-19 CN CN201010129552.4A patent/CN102190582B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1857771A (en) * | 2006-05-18 | 2006-11-08 | 复旦大学 | High selectivity catalyst for preparing tetrahydrofuran and its preparing process |
| CN101307042A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190582A (en) | 2011-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN102190582B (en) | Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol | |
| CN101544539B (en) | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate | |
| CN101927168B (en) | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof | |
| CN102806086A (en) | Preparation method of catalyst for coproducing isopropanol and methyl isobutyl ketone by acetone hydrogenation | |
| CN104557801A (en) | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst | |
| CN101735182B (en) | Process for continuously producing succinic anhydride through hydrogenation of maleic anhydride | |
| CN101768142A (en) | Method for catalysis-synthesizing 2,5-dicarbaldehyde by carbohydrate | |
| CN103265400A (en) | Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN102416325A (en) | Preparation method of isobutyl ketone synthesis catalyst | |
| CN104549347B (en) | Glycerine hydrogenation prepares catalyst of 1,2 propane diols and its preparation method and application | |
| CN102978012A (en) | Method of biodiesel preparation catalyzed by imidazole anionic type basic ionic liquid | |
| CN104193606A (en) | Technique for preparing acetone from synthetic gas | |
| CN109608304A (en) | A kind of method that furfural hydrogenation directly produces 1,2- pentanediol | |
| CN101733124B (en) | Catalyst for fixed bed hydrogenation for continuous production of fatty alcohol, preparation method thereof and application thereof | |
| US20130123549A1 (en) | Hydrogenation catalysts and the preparation processes thereof | |
| CN109796303A (en) | A kind of preparation method of isoprene | |
| WO2016180000A1 (en) | Two-step ethylene glycol and 1,2-propylene glycol preparation method using cellulose | |
| CN104230641B (en) | Produce the method for isopropyl benzene | |
| CN104230635B (en) | The method of hydrogenation of acetophenone ethylbenzene processed | |
| CN104230643B (en) | Prepare the method for isopropyl benzene | |
| CN110872208B (en) | Preparation method of cyclohexanol by coupling cyclohexane mixture dehydrogenation technology | |
| CN102649057B (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN110862302B (en) | Method for preparing 1, 4-butanediol by combining slurry bed hydrogenation and fixed bed hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. |