CN106366297B - The method of continuous production poly butylene succinate - Google Patents
The method of continuous production poly butylene succinate Download PDFInfo
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- CN106366297B CN106366297B CN201610970300.1A CN201610970300A CN106366297B CN 106366297 B CN106366297 B CN 106366297B CN 201610970300 A CN201610970300 A CN 201610970300A CN 106366297 B CN106366297 B CN 106366297B
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- butylene succinate
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- 239000004631 polybutylene succinate Substances 0.000 title claims abstract description 38
- 229920002961 polybutylene succinate Polymers 0.000 title claims abstract description 38
- -1 poly butylene succinate Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 24
- 238000010924 continuous production Methods 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 54
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 53
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000007791 liquid phase Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 44
- 238000005984 hydrogenation reaction Methods 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical group [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 12
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 11
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 7
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 7
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000001273 butane Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000011344 liquid material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 230000009469 supplementation Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002362 mulch Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of preparation method of the overall industrial chain of poly butylene succinate, on the one hand the quality of uncontrollable raw material in the prior art is overcome, on the other hand the problem of by-product small molecule is more, yield is relatively low in the prior art are overcome, so as to effectively reduce the production cost of poly butylene succinate.The present invention general reaction route be：Normal butane is gone out with C-4-fraction rectifying, liquid phase cis-butenedioic anhydride is produced with normal butane, succinic anhydride is produced by raw material of liquid phase cis-butenedioic anhydride, with succinic anhydride, 1,4 butanediols carry out ring-opening polymerisation with catalyst in nitrogen atmosphere, then polycondensation reaction is carried out under vacuum, that is, obtains target product poly butylene succinate.
Description
Technical field
The present invention relates to a kind of preparation method of poly butylene succinate, and in particular to one kind is using C-4-fraction as raw material
The method for synthesizing poly butylene succinate.
Background technology
Poly butylene succinate is a kind of important high molecular material, particularly as biodegradable material, easily by certainly
Enzyme in the multiple-microorganism or animal and plant body on right boundary decomposes, metabolism, while has good mechanical property and hot property, be from
Fundamentally solve one of effective way of white pollution problems.
The present invention be since C-4-fraction, since butane is raw material that is most cheap in C-4-fraction and being readily available, it
Relatively low with air mixed oxidization production cost, continuous production all by pipelined, forms overall liquid circulation, reduces more
Road intermediate link, improving product yield by a relatively large margin makes full biodegradable plastic mulch synchronous with conventional plastic mulch price,
Thoroughly break poly butylene succinate because price is high can not large area use, white pollution can be solved substantially and be difficult to solve
The problem of.
The content of the invention
Technical problem solved by the invention is a kind of preparation for the overall industrial chain for providing poly butylene succinate
Method, on the one hand overcomes the quality of uncontrollable raw material in the prior art, on the other hand overcomes small point of by-product in the prior art
The problem of son is more, yield is relatively low, so as to effectively reduce the production cost of poly butylene succinate.
The present invention general reaction route be：Normal butane is gone out with C-4-fraction rectifying, liquid phase cis-butenedioic anhydride is produced with normal butane, with
Liquid phase cis-butenedioic anhydride produces succinic anhydride for raw material, carries out open loop in nitrogen atmosphere with succinic anhydride, Isosorbide-5-Nitrae butanediol and catalyst and gathers
Close, then carry out polycondensation reaction under vacuum, that is, obtain target product poly butylene succinate.
Specifically include following steps：
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane；
In the step 1, rectifying goes out normal butane of the purity more than 95%.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
The step 2 includes：The mixed gas of normal butane and air is reacted in the reactor equipped with catalyst, reaction
Temperature control is 350-500 DEG C；In this step, the catalyst is vanadium phosphorus oxygen/foam SiC structural catalysts, by vanadium phosphorus oxygen
Coating and/or vanadium phosphorus oxygen crystal load on foam SiC carriers in can be made into the vanadium phosphorus oxygen/foam SiC structural catalysts.
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride；
It is respectively one using two reactors using the method for two sections of low-temp low-pressure reaction process in the step 3
Section reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen, which enter in first stage reactor, carries out partially catalyzed selection hydrogenation,
After reaction, remaining cis-butenedioic anhydride, the succinic anhydride of generation and solvent mixed liquor material enter second stage reactor and carry out catalysis choosing completely
Hydrogenation is selected, second stage reactor product obtains succinic anhydride product, solvent, hydrogen respectively after gas-liquid separation and rectifying, and gained is molten
Agent, hydrogen circulating and recovering；Wherein, hydrogenation reaction carries out under the conditions of low-temp low-pressure in first stage reactor, reaction temperature for 40~
80 DEG C, 0.2~2.0MPa of reaction pressure, hydrogenation reaction temperature is 60~120 DEG C in second stage reactor, reaction pressure 0.2~
2.0MPa, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature.
In the step 3, the catalyst of filling is loading type Pd catalysis in the first stage reactor, second stage reactor
Agent, the mass percentage composition of Supported Pd-Catalyst are：Catalyst in first stage reactor, Pd：0.01~1.0%, remaining
For carrier or auxiliary agent；Catalyst in second stage reactor, Pd：0.01~1.0%, remaining is carrier or coagent.
In the step 3, the solvent added in first stage reactor is dimethyl succinate, diethyl succinate, acetic acid
One or more in ethyl ester, butyl acetate.
Step 4：Using 1,4 butanediols and step 3 gained succinic anhydride poly butylene succinate is prepared as raw material；
Step 4.1：Polymerized monomer succinic anhydride, Isosorbide-5-Nitrae butanediol and catalyst are subjected to ring-opening polymerisation in nitrogen atmosphere,
180-280 DEG C of reaction temperature, when reaction time 1-5 is small；
In the step 4.1, the preferred molar ratio of succinic anhydride and Isosorbide-5-Nitrae butanediol is 1:1.1~1.4.
Catalyst employed in the step 4.1 is benzene sulfonic acid, zinc acetate, p-methyl benzenesulfonic acid, butyl titanate, three oxygen
Change the one or more in two antimony, manganese acetate, four butyl ester of germanic acid, cadmium acetate.
Step 4.2, polycondensation reaction is carried out under vacuum, vacuum 20-300Pa, 210-260 DEG C of reaction temperature, instead
When 1-6 is small between seasonable, that is, obtain target product poly butylene succinate.
In the step 4.2 add benzene sulfonic acid, zinc acetate, p-methyl benzenesulfonic acid, antimony oxide, one kind in manganese acetate or
It is several to be used as catalyst.
After adopting the above technical scheme, the present invention prepares poly-succinic fourth using C-4-fraction as raw material by successive reaction
Diol ester.Continuous production all by pipelined, forms overall liquid circulation, reduces multiple tracks intermediate link, reduces reaction
Cost, reduces environmental pollution.Low production cost, products obtained therefrom stable quality, yield are higher.
In addition, the acidity of succinic anhydride is far smaller than succinic acid, the corrosion to equipment is small, can reduce to metal material
Demand, i.e., save a large amount of expenses in fixed equipment investment and maintenance of equipment, that is, reduces product cost.
The present invention is raw material using C-4-fraction, and source is easy to get, and the requirement of product is fully achieved in its quality；In C-4-fraction
Normal butane gas can be easily separated, price is low；Use value additional income is improved after C-4-fraction.
Embodiment
The embodiment of the present invention is illustrated below.
The present invention general reaction route be：Normal butane is gone out with C-4-fraction rectifying, liquid phase cis-butenedioic anhydride is produced with normal butane, with
Liquid phase cis-butenedioic anhydride produces succinic anhydride for raw material, carries out open loop in nitrogen atmosphere with succinic anhydride, Isosorbide-5-Nitrae butanediol and catalyst and gathers
Close, then carry out polycondensation reaction under vacuum, that is, obtain target product poly butylene succinate.Concrete technology flow process bag
Include：
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane.
The C-4-fraction comes from the accessory substance of petroleum refining process generation, such as refinery gas and petrochemical industry production
Cracking gas of hydrocarbon cracking etc., its source are easy to get, and raw material is sufficient；C-4-fraction is taken into extracting rectifying, chemical absorbing and physics
The method that absorption etc. is combined with rectifying, isolates normal butane gas of the purity more than 95%.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
Normal butane prepare liquid phase cis-butenedioic anhydride technique be：The mixed gas of normal butane and air is in the reactor equipped with catalyst
Middle reaction, reaction temperature control are 350-500 DEG C；In this step, the catalyst is vanadium phosphorus oxygen/foam SiC structured catalysts
Agent, vanadium phosphorus oxygen coating and/or vanadium phosphorus oxygen crystal load are tied in can be made into the vanadium phosphorus oxygen/foam SiC on foam SiC carriers
Structure catalyst.
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride.
Liquid phase maleic anhydride hydrogenation prepares method of the succinic anhydride reaction using two sections of low-temp low-pressure reaction process, anti-using two
Device is answered, is respectively first stage reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen, which enter, carries out part in first stage reactor
Catalysis selective hydrogenation, after reaction, remaining cis-butenedioic anhydride, generation succinic anhydride and solvent mixed liquor material enter second stage reactor into
The complete catalysis selective hydrogenation of row, second stage reactor product obtained respectively after gas-liquid separation and rectifying succinic anhydride product, solvent,
Hydrogen, gained solvent, hydrogen circulating and recovering；Wherein, hydrogenation reaction carries out under the conditions of low-temp low-pressure in first stage reactor, reaction
Temperature is 40~80 DEG C, 0.2~2.0MPa of reaction pressure, and hydrogenation reaction temperature is 60~120 DEG C in second stage reactor, reaction pressure
0.2~2.0MPa of power, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature；In this step, using hydrogen
Carry out removing heat, hydrogen is passed through after reducing reaction heat in first stage reactor and second stage reactor and recycles after gas-liquid separator separates
Use, a small amount of fresh hydrogen is only required supplementation with reaction process and is used for hydrogenation reaction, in this step, circulating hydrogen is suitable with liquid phase
The molar ratio of acid anhydride is 30~200：1, the fresh hydrogen of supplement and the molar ratio 1.0~1.5 of liquid phase cis-butenedioic anhydride：1,
The catalyst of filling is Supported Pd-Catalyst in the first stage reactor, second stage reactor, and loading type Pd is urged
The mass percentage composition of agent is：Catalyst in first stage reactor, Pd：0.01~1.0%, remaining is carrier or auxiliary agent；
Catalyst in second stage reactor, Pd：0.01~1.0%, remaining is carrier or coagent,
In this step, the solvent added in the first stage reactor is dimethyl succinate, diethyl succinate, acetic acid second
One or more in ester, butyl acetate.
Step 4：Using 1,4 butanediols and step 3 gained succinic anhydride poly butylene succinate is prepared as raw material.
Step 4.1：Polymerized monomer succinic anhydride, Isosorbide-5-Nitrae butanediol and catalyst are subjected to ring-opening polymerisation in nitrogen atmosphere,
180-260 DEG C of reaction temperature, when reaction time 1-5 is small；
In step 4.1, the preferred molar ratio of succinic anhydride and Isosorbide-5-Nitrae butanediol is 1:1.1~1.4；
Catalyst employed in step 4.1 is benzene sulfonic acid, zinc acetate, p-methyl benzenesulfonic acid, butyl titanate, three oxidations two
One or more in antimony, manganese acetate, four butyl ester of germanic acid, cadmium acetate.
Step 4.2, polycondensation reaction is carried out under vacuum, vacuum 20-300Pa, 210-260 DEG C of reaction temperature, instead
When 1-6 is small between seasonable, that is, obtain target product poly butylene succinate.
Preferably, added in the step 4.2 in benzene sulfonic acid, zinc acetate, p-methyl benzenesulfonic acid, antimony oxide, manganese acetate
One or more as catalyst.
Embodiment 1
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane.
The C-4-fraction comes from the accessory substance of petroleum refining process generation, such as refinery gas and petrochemical industry production
Cracking gas of hydrocarbon cracking etc., its source are easy to get, and raw material is sufficient；C-4-fraction is taken into extracting rectifying, chemical absorbing and physics
The method that absorption etc. is combined with rectifying, isolates normal butane gas of the purity more than 95%.
In this step, with 10,000,000 tons of oil refining C-4-fraction raw materials of Anqing Petrochemical Company, the normal butane gas that purity is 95.5% is made
Body.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
The reaction of n butane oxidation liquid phase cis-butenedioic anhydride carries out on fixed bed reactors, and reaction temperature is 350 DEG C --- and 450 DEG C,
Reaction raw materials are normal butane and air, and normal butane gaseous volume accounts for total tolerance（Normal butane volume and volume of air）Ratio be
2.5%.Feed volume air speed is 150h-1, generally 1000ml/min or so, notices that the reading of flowmeter refers to gas in standard
Volume under state, is not volume or mass flow under practical measurement state, and the reading and gas temperature of flowmeter, pressure do not have
There are much relations.
In this step, the catalyst is vanadium phosphorus oxygen/foam SiC structural catalysts, by vanadium phosphorus oxygen coating and/or vanadium phosphorus
Oxygen crystal load on foam SiC carriers i.e. can be made into the vanadium phosphorus oxygen/foam SiC structural catalysts.
Using V-O-P catalyst, due to that can make full use of raw material, and the weight yield of raw material is higher, air first by
Then compressor compresses are controlled in air storage tank by pressure reducing valve to air flow meter, the reading of flowmeter by display instrument.
Step 3：Succinic anhydride is prepared with step 2 gained cis-butenedioic anhydride.
Liquid phase maleic anhydride hydrogenation prepares method of the succinic anhydride reaction using two sections of low-temp low-pressure reaction process, anti-using two
Device is answered, is respectively first stage reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen, which enter, carries out part in first stage reactor
Catalysis selective hydrogenation, after reaction, remaining cis-butenedioic anhydride, generation succinic anhydride and solvent mixed liquor material enter second stage reactor into
The complete catalysis selective hydrogenation of row, second stage reactor product obtained respectively after gas-liquid separation and rectifying succinic anhydride product, solvent,
Hydrogen, gained solvent circulating and recovering；Wherein, hydrogenation reaction carries out under the conditions of low-temp low-pressure in first stage reactor, reaction temperature
For 40~80 DEG C, 0.2~2.0MPa of reaction pressure, hydrogenation reaction temperature is 60~120 DEG C in second stage reactor, reaction pressure
0.2~2.0MPa, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature；In this step, using hydrogen into
Row removes heat, and hydrogen, which is passed through to recycle after gas-liquid separator separates after reduction reaction heat in first stage reactor and second stage reactor, to be made
With only requiring supplementation with a small amount of fresh hydrogen in reaction process and be used for hydrogenation reaction, in this step, circulating hydrogen and cis-butenedioic anhydride rub
You are than being 30~200：1, the fresh hydrogen of supplement and the molar ratio 1.0~1.5 of cis-butenedioic anhydride：1,
The catalyst of filling is Supported Pd-Catalyst in the first stage reactor, second stage reactor, and loading type Pd is urged
The mass percentage composition of agent is：Catalyst in first stage reactor, Pd：0.01~1.0%, remaining is carrier or auxiliary agent；
Catalyst in second stage reactor, Pd：0.01~1.0%, remaining is carrier or coagent.
In this step, the solvent added in the reactor is dimethyl succinate, and liquid phase cis-butenedioic anhydride, the mass ratio of solvent are
1：10.
Step 4：Using 1,4 butanediols and step 3 gained succinic anhydride poly butylene succinate is prepared as raw material.
Concrete technology step is：
Step 4.1：With heating unit, agitating device, temperature controller reaction kettle in be separately added into succinic anhydride
150.0 kilograms (1500mol), 1,4-butanediol 148.7 kilograms (1650mol), 0.1 kilogram of benzene sulfonic acid, 0.1 kilogram of zinc acetate,
Stirring heats up under nitrogen atmosphere, 180 DEG C of controlling reaction temperature under normal pressure, when reaction 3 is small.
Step 4.2,0.05 kilogram of 0.05 kilogram of benzene sulfonic acid and zinc acetate are added, is then heated up, it is absolute pressure to control vacuum
300Pa, 260 DEG C of reaction temperature, continue reaction 4 it is small when, obtain 253.2 kilograms of poly butylene succinate, product yield
84.8%.After testing, its weight average molecular weight Mw values are 83.5k, and molecular weight distribution mw/mn value is 1.9.
Embodiment 2
Step 1：Using C-4-fraction as raw material, normal butane gas of the purity more than 95% is isolated.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
Using V-O-P catalyst, butane arrives mass flowmenter, and experimental condition by pressure reducing valve, generally controls
System and the volume ratio of air are less than 1.6%, to avoid explosion danger.The reading of butane gas mass flowmenter need to be multiplied by
0.29, it is only the normal volume of butane.
Butane and air respectively enter the top of blending tank, and are mixed in tank, when the pressure of mixed gas reaches
During 0.2Mpa, it could start to produce.The reactor feed gas prepared comes out from the lower part of tank, has respectively entered pressure maintaining valve, pressure gauge
With gas six-way valve, subsequently into the spinner flowmeter of each reactor, the flow into reactor can be adjusted as desired.
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride.
This step uses two reactors, respectively first stage reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen
Partially catalyzed selection hydrogenation is carried out in into first stage reactor, after reaction, remaining cis-butenedioic anhydride, the succinic anhydride of generation and solvent mix
Close liquid material and enter the complete catalysis selective hydrogenation of second stage reactor progress, second stage reactor product divides after gas-liquid separation and rectifying
Not Huo get succinic anhydride product, solvent, hydrogen, gained solvent circulating and recovering；Wherein, in first stage reactor hydrogenation reaction in low temperature
Carried out under lower pressure, reaction temperature is 40~80 DEG C, 0.2~2.0MPa of reaction pressure, hydrogenation reaction temperature in second stage reactor
Spend for 60~120 DEG C, 0.2~2.0MPa of reaction pressure, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature
Degree；In this step, carry out removing heat using hydrogen, hydrogen is passed through in first stage reactor and second stage reactor after reduction reaction heat through gas
It is recycled after liquid/gas separator separation, a small amount of fresh hydrogen is only required supplementation with reaction process and is used for hydrogenation reaction, this step
In rapid, the molar ratio of circulating hydrogen and cis-butenedioic anhydride is 30~200：1, the fresh hydrogen of supplement and the molar ratio 1.0~1.5 of cis-butenedioic anhydride：
1。
In the step 3, the solvent added in first stage reactor is dimethyl succinate, diethyl succinate.Liquid phase
Cis-butenedioic anhydride, the mass ratio of solvent are 1：10.
Step 4：Using step 3 gained succinic anhydride, 1,4 butanediols poly butylene succinate is prepared as raw material.
Step 4.1：With heating unit, agitating device, temperature controller reaction kettle in be separately added into succinic anhydride
150.0 kilograms (1500mol), 1,4-butanediol 141.5 kilograms (1570mol), 0.1 kilogram of p-methyl benzenesulfonic acid, butyl titanate
0.1 kilogram, stirring under nitrogen atmosphere heats up, 190 DEG C of controlling reaction temperature under normal pressure, when reaction 2 is small.
Step 4.2,0.05 kilogram of 0.05 kilogram of benzene sulfonic acid and butyl titanate are added, is then heated up, controls the vacuum to be
Absolute pressure 30Pa, 260 DEG C of reaction temperature, continue reaction 3 it is small when, obtain 256.2 kilograms of poly butylene succinate, product yield
87.9%.After testing, its weight average molecular weight Mw values are 145.5k, molecular weight distribution mw/mn 1.9.
Embodiment 3
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
Using V-O-P catalyst, the reaction of n butane oxidation liquid phase cis-butenedioic anhydride carries out on fixed bed reactors.React bar
Part is as follows：Reaction temperature is 500 DEG C, and reaction raw materials are normal butane and air, use nitrogen as carrier gas, normal butane gaseous state body
Product accounts for total tolerance（Normal butane volume, air and nitrogen volume）Ratio be 1.25%.Feed volume air speed is 2000h-1。
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride.
This step uses two reactors, respectively first stage reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen
Partially catalyzed selection hydrogenation is carried out in into first stage reactor, after reaction, remaining cis-butenedioic anhydride, the succinic anhydride of generation and solvent mix
Close liquid material and enter the complete catalysis selective hydrogenation of second stage reactor progress, second stage reactor product divides after gas-liquid separation and rectifying
Not Huo get succinic anhydride product, solvent, hydrogen, gained solvent circulating and recovering；Wherein, in first stage reactor hydrogenation reaction in low temperature
Carried out under lower pressure, reaction temperature is 40~80 DEG C, 0.2~2.0MPa of reaction pressure, hydrogenation reaction temperature in second stage reactor
Spend for 60~120 DEG C, 0.2~2.0MPa of reaction pressure, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature
Degree.
In the step 3, the solvent that adds in first stage reactor is ethyl acetate, liquid phase cis-butenedioic anhydride, the mass ratio of solvent
For 1：10.
Step 4：Poly butylene succinate is prepared as raw material using 1,4 butanediols, step 3 gained succinic anhydride.
Step 4.1：With heating unit, agitating device, temperature controller reaction kettle in be separately added into succinic anhydride
150.0 kilograms (1500mol), 1,4-butanediol 135.2 kilograms (1500mol), 0.1 kilogram of benzene sulfonic acid, antimony oxide 0.2 thousand
Gram, 0.1 kilogram of manganese acetate, under nitrogen atmosphere stirring heats up, 190 DEG C of controlling reaction temperature under normal pressure, when reaction 2 is small.
Step 4.2：Add 0.05 kilogram of p-methyl benzenesulfonic acid, 0.1 kilogram of antimony oxide, 0.05 kilogram of manganese acetate, so
After heat up, it is absolute pressure 30Pa to control vacuum, 280 DEG C of reaction temperature, continue reaction 5 it is small when, obtain poly butylene succinate
254.2 kilograms, product yield 89.2%.After testing, its weight average molecular weight Mw values are 101.2k, and molecular weight distribution mw/mn value is
2.0。
Embodiment 4
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
Using V-O-P catalyst, the reaction of n butane oxidation liquid phase cis-butenedioic anhydride carries out on fixed bed reactors.React bar
Part is as follows：Reaction temperature is 400 DEG C, and reaction raw materials are normal butane and air, and normal butane gaseous volume accounts for total tolerance（Normal butane
Volume and volume of air）Ratio be 2.5%.Feed volume air speed is 1500h-1。
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride.
This step uses two reactors, respectively first stage reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen
Partially catalyzed selection hydrogenation is carried out in into first stage reactor, after reaction, remaining cis-butenedioic anhydride, the succinic anhydride of generation and solvent mix
Close liquid material and enter the complete catalysis selective hydrogenation of second stage reactor progress, second stage reactor product divides after gas-liquid separation and rectifying
Not Huo get succinic anhydride product, solvent, hydrogen, gained solvent circulating and recovering；Wherein, in first stage reactor hydrogenation reaction in low temperature
Carried out under lower pressure, reaction temperature is 40~80 DEG C, 0.2~2.0MPa of reaction pressure, hydrogenation reaction temperature in second stage reactor
Spend for 60~120 DEG C, 0.2~2.0MPa of reaction pressure, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature
Degree.
In this step, the solvent added in the reactor is dimethyl succinate, and liquid phase cis-butenedioic anhydride, the mass ratio of solvent are
1：10.
Step 4：Poly butylene succinate is prepared as raw material using 1,4 butanediols, step 3 gained succinic anhydride.
Step 4.1：With heating unit, agitating device, temperature controller reaction kettle in be separately added into succinic anhydride
150.0 kilograms (1500mol), 1,4-butanediol 162.2 kilograms (1800mol), 0.2 kilogram of p-methyl benzenesulfonic acid, four butyl ester of germanic acid
0.2 kilogram, stirring under nitrogen atmosphere heats up, 190 DEG C of controlling reaction temperature under normal pressure, when reaction 2 is small.
Step 4.2：Then heat up, it is absolute pressure 30Pa to control vacuum, 220 DEG C of reaction temperature, continue reaction 5 it is small when,
255.6 kilograms of poly butylene succinate is obtained, product yield 81.9%, after testing, its weight average molecular weight Mw values are 68.8k,
Molecular weight distribution mw/mn value is 2.1.
Embodiment 5
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane.
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane.
The reaction of n butane oxidation liquid phase cis-butenedioic anhydride carries out on fixed bed reactors.Reaction condition is as follows：Reaction temperature is
400 DEG C, reaction raw materials are normal butane and air, and normal butane gaseous volume accounts for total tolerance（Normal butane volume and volume of air）'s
Ratio is 2.5%.Feed volume air speed is 2000h-1。
In this step, V-O-P specificity of catalyst is as follows：Vanadium phosphorus oxygen crystalline size is 50nm, and P/V atomic ratios are 0.9, vanadium
10 μm of phosphorus oxygen coating layer thickness, vanadium phosphorus oxygen crystal load amount are 10 weight %.The aperture of foam SiC carriers is 1mm, porosity
65%.The specific surface area of vanadium phosphorus oxygen/foam SiC structural catalysts is 53.7m2·g-1, micro pore surface area 25.6m2·g-1, the external surface area that composite material is measured with t-plot methods is 28.3m2·g-1.Have in vanadium phosphorus oxygen coating between vanadium phosphorus oxygen crystal
There is high intercrystalline pore rate, vanadium phosphorus oxygen crystal overlaps the mesopore volume to be formed accounts for total pore volume 45%.
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride.
This step uses two reactors, respectively first stage reactor and second stage reactor, liquid phase cis-butenedioic anhydride, solvent and hydrogen
Partially catalyzed selection hydrogenation is carried out in into first stage reactor, after reaction, remaining cis-butenedioic anhydride, the succinic anhydride of generation and solvent mix
Close liquid material and enter the complete catalysis selective hydrogenation of second stage reactor progress, second stage reactor product divides after gas-liquid separation and rectifying
Not Huo get succinic anhydride product, solvent, hydrogen, gained solvent circulating and recovering；Wherein, in first stage reactor hydrogenation reaction in low temperature
Carried out under lower pressure, reaction temperature is 40~80 DEG C, 0.2~2.0MPa of reaction pressure, hydrogenation reaction temperature in second stage reactor
Spend for 60~120 DEG C, 0.2~2.0MPa of reaction pressure, and second stage reactor interior reaction temperature is higher than first stage reactor reaction temperature
Degree.
In this step, the solvent added in the reactor is dimethyl succinate, and liquid phase cis-butenedioic anhydride, the mass ratio of solvent are
1：10.
Step 4：Poly butylene succinate is prepared as raw material using 1,4 butanediols, step 3 gained succinic anhydride.
Step 4.1：With heating unit, agitating device, temperature controller reaction kettle in be separately added into succinic anhydride
150.0 kilograms (1500mol), 1,4-butanediol 162.2 kilograms (1800mol), 0.2 kilogram of benzene sulfonic acid, antimony oxide 0.2 thousand
Gram, 0.2 kilogram of cadmium acetate, under nitrogen atmosphere stirring heats up, 190 DEG C of controlling reaction temperature under normal pressure, when reaction 3 is small.
Step 4.2：Then heat up, it is absolute pressure 100Pa to control vacuum, 270 DEG C of reaction temperature, continue reaction 6 it is small when,
256.3 kilograms of poly butylene succinate is obtained, product yield 82.1%, after testing, its weight average molecular weight Mw values are 113.9k,
Molecular weight distribution mw/mn value is 2.2.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although ginseng
The present invention is described in detail according to preferred embodiment, it will be understood by those of ordinary skill in the art that, can be to invention
Technical solution technical scheme is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention, it should all cover
In scope of the presently claimed invention.
Claims (9)
1. a kind of method of continuous production poly butylene succinate, comprises the following steps：
Step 1：Using C-4-fraction as raw material, rectifying goes out normal butane；
Step 2：Liquid phase cis-butenedioic anhydride is prepared with step 1 gained normal butane；
Step 3：Succinic anhydride is prepared with step 2 gained liquid phase cis-butenedioic anhydride；
Step 4：Poly butylene succinate is prepared as raw material using 1,4- butanediols and step 3 gained succinic anhydride；
Step 4.1：Polymerized monomer succinic anhydride, 1,4-butanediol and catalyst are subjected to ring-opening polymerisation in nitrogen atmosphere, instead
180-260 DEG C of temperature is answered, when reaction time 1-5 is small；
Step 4.2, polycondensation reaction is carried out under vacuum, vacuum 20-300Pa, 210-280 DEG C of reaction temperature, during reaction
Between 1-6 it is small when, that is, obtain target product poly butylene succinate.
2. the method for continuous production poly butylene succinate as claimed in claim 1, it is characterised in that：The step 1
In, rectifying goes out normal butane of the purity more than 95%.
3. the method for continuous production poly butylene succinate as claimed in claim 1, it is characterised in that：The step 2
Including：The mixed gas of normal butane and air is reacted in the reactor equipped with catalyst, and reaction temperature control is 350-500
℃；In this step, the catalyst is vanadium phosphorus oxygen/foam SiC structural catalysts.
4. the method for continuous production poly butylene succinate as claimed in claim 1, it is characterised in that：The step 3
In, using the method for two sections of low-temp low-pressure reaction process, reacted in first stage reactor and second stage reactor, liquid phase is suitable
Acid anhydride, solvent and hydrogen, which enter in first stage reactor, carries out partially catalyzed selection hydrogenation, after reaction, remaining cis-butenedioic anhydride, the fourth of generation
Dicarboxylic anhydride and solvent mixed liquor material enter second stage reactor and carry out complete catalysis selective hydrogenation, and second stage reactor product is through gas-liquid
Succinic anhydride product, solvent, hydrogen, gained solvent, hydrogen circulating and recovering are obtained respectively after separation and rectifying；Wherein, one section it is anti-
Hydrogenation reaction in device is answered to be carried out under the conditions of low-temp low-pressure, reaction temperature is 40~80 DEG C, reaction pressure 0.2~2.0MPa, two
Hydrogenation reaction temperature is 60~120 DEG C, 0.2~2.0MPa of reaction pressure in section reactor, and second stage reactor interior reaction temperature
Higher than first stage reactor reaction temperature.
5. the method for continuous production poly butylene succinate as claimed in claim 4, it is characterised in that：The step 3
In, filling Supported Pd-Catalyst, the mass percent group of Supported Pd-Catalyst in the first stage reactor, second stage reactor
Become：Catalyst in first stage reactor, Pd：0.01~1.0%, remaining is carrier or auxiliary agent；Catalysis in second stage reactor
Agent, Pd：0.01~1.0%, remaining is carrier or coagent.
6. the method for continuous production poly butylene succinate as claimed in claim 4, it is characterised in that：The step 3
In, the solvent added in first stage reactor is one in dimethyl succinate, diethyl succinate, ethyl acetate, butyl acetate
Kind is several.
7. the method for continuous production poly butylene succinate as claimed in claim 1, it is characterised in that：The step 4.1
In, the preferred molar ratio of succinic anhydride and 1,4-butanediol is 1:1.1~1.4.
8. the method for continuous production poly butylene succinate as claimed in claim 1, it is characterised in that：The step 4.1
Employed in catalyst be benzene sulfonic acid, zinc acetate, p-methyl benzenesulfonic acid, butyl titanate, antimony oxide, manganese acetate, germanic acid
One or more in four butyl esters, cadmium acetate.
9. the method for continuous production poly butylene succinate as claimed in claim 1, it is characterised in that：The step 4.2
The middle one or more added in benzene sulfonic acid, zinc acetate, p-methyl benzenesulfonic acid, antimony oxide, manganese acetate are as catalyst.
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Application publication date: 20170201 Assignee: Beijing Zhiling Technology Co.,Ltd. Assignor: Beijing Zhongzhi Environmental Protection Technology Co.,Ltd. Contract record no.: X2024980005061 Denomination of invention: Method for continuous production of polybutylene succinate Granted publication date: 20180427 License type: Common License Record date: 20240429 |