CN116178105B - Method for improving neopentyl glycol yield by catalytic decomposition of quaternary congenital ester - Google Patents
Method for improving neopentyl glycol yield by catalytic decomposition of quaternary congenital ester Download PDFInfo
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- CN116178105B CN116178105B CN202211570246.3A CN202211570246A CN116178105B CN 116178105 B CN116178105 B CN 116178105B CN 202211570246 A CN202211570246 A CN 202211570246A CN 116178105 B CN116178105 B CN 116178105B
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000000034 method Methods 0.000 title claims abstract description 94
- 150000002148 esters Chemical class 0.000 title claims abstract description 86
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 41
- 206010010356 Congenital anomaly Diseases 0.000 title abstract description 3
- 239000000047 product Substances 0.000 claims abstract description 58
- 239000012043 crude product Substances 0.000 claims abstract description 20
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims description 91
- 239000003054 catalyst Substances 0.000 claims description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 229920001577 copolymer Polymers 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000007791 liquid phase Substances 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 26
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 26
- 238000000354 decomposition reaction Methods 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 25
- 239000002699 waste material Substances 0.000 claims description 23
- 230000008961 swelling Effects 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- 238000012856 packing Methods 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 15
- 230000005494 condensation Effects 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 238000005576 amination reaction Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 7
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 3
- 238000004821 distillation Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000000039 congener Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for improving the yield of neopentyl glycol by catalytically decomposing quaternary ancestral ester, which comprises the following steps: (1) Heavy component of the neopentyl glycol product tower is subjected to heavy removal treatment to obtain a light component gas phase; (2) Condensing the light component gas phase obtained in the step (1) to obtain condensate; (3) Rectifying and recycling the condensate obtained in the step (2) to obtain a heavy component containing quaternary ancestral ester; (4) And (3) carrying out catalytic decomposition on the heavy component containing the quaternary ancestral ester obtained in the step (3) to obtain a neopentyl glycol crude product. The method provided by the invention can effectively decompose the quaternary congenital ester to generate the neopentyl glycol product, can increase the product yield and saves the energy consumption.
Description
Technical Field
The invention relates to the technical field of neopentyl glycol production, in particular to a method for improving the yield of neopentyl glycol by catalytically decomposing quaternary ancestral ester.
Background
Neopentyl glycol (2, 2-dimethyl-1, 3-propanediol, abbreviated as NPG) is an excellent solvent which has good water resistance, solvent resistance and weather resistance, is mainly used for unsaturated polyester resin, oil-free alkyd resin, polyurethane foam plastic, elastomer plasticizer, high-grade lubricant additive and other fine chemicals, and has very broad development prospect.
Currently, there are many industrial processes for the preparation of neopentyl glycol, among which disproportionation and condensation hydrogenation are widely used. Compared with a disproportionation method, the condensation hydrogenation method has the advantages of short flow, good product quality, small separation difficulty, environment-friendly process and the like, so that the condensation hydrogenation method is widely used. However, during the preparation of neopentyl glycol by the condensation hydrogenation process, the bottoms of the product column may produce a heavy ends effluent containing about 40% neopentyl glycol and 40% quaternary ancestral ester. Taking an NPG plant producing 4 ten thousand tons per year as an example, the amount of waste liquid produced by the NPG plant reaches 1000 tons per year, thereby causing direct loss of neopentyl glycol product to reach 420 ten thousand yuan per year.
CN109761756a discloses a process for extracting neopentyl glycol and quaternary ancestral esters from neopentyl glycol waste liquid, which adopts ethyl butyrate as a solvent for recrystallization, and separates neopentyl glycol and quaternary ancestral esters by using a crystallization method. However, this separation method is not only costly but also has very limited productivity.
CN109400473a discloses a method for preparing neopentyl glycol hydroxypivalate monoester and co-producing neopentyl glycol, the method comprises the steps of generating a mixture mainly comprising neopentyl glycol hydroxypivalate monoester and neopentyl glycol from isobutyraldehyde and formaldehyde solution under the action of an alkaline catalyst, then removing the catalyst through neutralization or filtration, and separating by rectification to obtain neopentyl glycol monoester and neopentyl glycol hydroxypivalate monoester respectively. The preparation method can separate neopentyl glycol through rectification, but has the advantages of high energy consumption, difficult storage and disproportionate output and input of actual production.
Thus, how to effectively separate neopentyl glycol from quaternary ancestral esters and to increase the yield of neopentyl glycol is a problem to be solved at present.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a method for improving the yield of neopentyl glycol by catalytically decomposing quaternary ancestral ester.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a method for improving the yield of neopentyl glycol by catalytically decomposing quaternary ancestral ester, which comprises the following steps:
(1) Heavy component of the neopentyl glycol product tower is subjected to heavy removal treatment to obtain a light component gas phase;
(2) Condensing the light component gas phase obtained in the step (1) to obtain condensate;
(3) Rectifying and recycling the condensate obtained in the step (2) to obtain a heavy component containing quaternary ancestral ester;
(4) And (3) carrying out catalytic decomposition on the heavy component containing the quaternary ancestral ester obtained in the step (3) to obtain a neopentyl glycol crude product.
The method provided by the invention is based on the process of producing neopentyl glycol by a condensation hydrogenation method, and the condensation hydrogenation method generally generates heavy components containing quaternary ancestral ester and neopentyl glycol at the tower bottom of a product tower, so that the heavy components are difficult to directly use, and serious product loss is caused. Firstly, separating tar substances and light component gas phase through heavy removal treatment, removing heavy component tar substances, wherein the tar substances can be sent to incineration treatment to prevent the tar substances from being attached to the catalyst in the step (4) to cause difficult catalytic decomposition, and the light component gas phase contains quaternary ancestral ester and neopentyl glycol; then condensing the light component gas phase, rectifying and recovering the obtained condensate to obtain a neopentyl glycol product, improving the product yield, and avoiding energy waste caused by the product entering the next catalytic decomposition or product loss caused by transesterification; and finally, carrying out catalytic decomposition on the heavy component containing the quaternary ancestral ester obtained by rectification recovery to obtain a crude product, and further improving the product yield. Therefore, the method provided by the invention can recover and prepare the neopentyl glycol from the quaternary ancestral ester in the heavy component by sequentially carrying out dehydrogenation treatment, condensation, rectification recovery and catalytic decomposition on the heavy component in the neopentyl glycol product tower, so that the yield of the neopentyl glycol is improved, and the treatment energy consumption and the treatment cost are reduced.
Preferably, the de-duplication treatment is performed in a wiped film evaporator.
Preferably, the operating temperature of the stripping treatment in step (1) is 155-170 ℃, for example 155 ℃, 156 ℃, 158 ℃, 160 ℃, 162 ℃, 164 ℃, 166 ℃, 168 ℃ or 170 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 160-165 ℃.
Preferably, the operating pressure of the stripping treatment is 0.3-1kPaG, for example, 0.3kPaG, 0.4kPaG, 5kPaG, 0.6kPaG, 0.7kPaG, 0.8kPaG, 0.9kPaG or 1.0kPaG, but not limited to the recited values, and other non-recited values within the range of values are equally suitable, preferably 0.3-0.5kPaG.
Preferably, the weight percentage of the quaternary congener esters in the light component gas phase obtained by the heavy removal treatment in the step (1) is 40-45%, for example 40%, 40.5%, 41%, 41.5%, 42%, 42.5%, 43%, 43.5%, 44%, 44.5% or 45%, but not limited to the recited values, other non-recited values in the range of values are equally applicable
In the invention, the operation temperature and the operation pressure of the heavy component removal treatment are preferably controlled, so that tar substances can be further removed to obtain a light component gas phase.
Preferably, the weight percent of neopentyl glycol in the light component gas phase obtained by the weight removal treatment is 35-45%, such as 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44% or 45%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the de-duplication treatment of step (1) also results in a heavy fraction liquid phase.
Preferably, the heavy fraction liquid phase contains tar.
Preferably, the tar comprises 10-15% by mass of the heavy component of the neopentyl glycol product column, for example 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%, but not limited to the values recited, other values not recited in the range of values being equally applicable.
Preferably, the mass percentage of the quaternary ancestral ester in the quaternary ancestral ester-containing heavy component recovered by the rectification in the step (3) is 75-85%, for example, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84% or 85%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the rectification recovery also yields a light fraction comprising neopentyl glycol.
Preferably, the neopentyl glycol content in the light component containing neopentyl glycol recovered by rectification is 95-99%, for example, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% or 99%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, a part of the light component containing neopentyl glycol is refluxed and a part of the light component containing neopentyl glycol is extracted to obtain a neopentyl glycol product.
Preferably, the rectification recovery of step (3) is carried out in a recovery column.
In the invention, the condensing medium at the top of the recovery tower can generate 2S steam for heat preservation and heat tracing of the pipeline.
The temperature of the recovery column bottom is preferably 185 to 195 ℃, and may be 185 to 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, or 195 ℃, for example, but not limited to the values listed, and other values not listed in the numerical range are applicable, and preferably 185 to 190 ℃.
Preferably, the operating pressure at the top of the recovery column is 5-8kPaG, which may be, for example, 5kPaG, 5.5kPaG, 6kPaG, 6.5kPaG, 7kPaG, 7.5kPaG or 8kPaG, but is not limited to the values recited, and other values not recited in the range of values are equally applicable, preferably 6-8kPaG.
Preferably, the packing of the recovery column comprises wire mesh structured packing.
Preferably, the height of the wire mesh structured packing is 10-15m, for example, 10m, 11m, 12m, 13m, 14m or 15m, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 10-12m.
Preferably, the reflux ratio recovered by the rectification is 8-15, for example, 8, 9, 10, 11, 12, 13, 14 or 15, but not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 10-12.
Preferably, the catalytic decomposition temperature in step (4) is 80-90 ℃, for example, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, or 90 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the present invention, it is preferable to control the catalytic decomposition temperature within a specific range, so that not only the quaternary ancestral ester can have good fluidity, but also neopentyl glycol obtained after the decomposition can be recovered.
Preferably, the catalytic decomposition is carried out in a decomposition column.
Preferably, the diameter of the decomposing column is 0.4-0.6m, for example, 0.4m, 0.45m, 0.5m, 0.55m or 0.6m, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the decomposing column is filled with a catalyst.
In the invention, the catalyst comprises an alkaline resin catalyst, and adopts a mode of lower inlet and upper outlet.
Preferably, the volume of the catalyst filled in the decomposing column is 0.2-0.3m 3, for example, 0.2m 3、0.22m3、0.24m3、0.26m3、0.28m3 or 0.3m 3, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the residence time of the quaternary-containing congener ester heavy component in the decomposition tower is 1-1.2h, for example, 1h, 1.02h, 1.04h, 1.06h, 1.08h, 1.10h, 1.12h, 1.14h, 1.16h, 1.18h or 1.2h, but not limited to the recited values, other non-recited values in the range of values are equally applicable.
In the present invention, it is preferable to control the residence time within a specific range, so that the reaction can be further promoted to be completely carried out while avoiding occurrence of side reactions, and the yield of neopentyl glycol can be improved.
Preferably, the top of the decomposing column is provided with a neopentyl glycol crude product.
Preferably, the neopentyl glycol crude product is returned to the de-weight treatment of step (1).
Preferably, the tower bottom of the decomposing tower is used for obtaining waste liquid containing quaternary ancestral ester.
Preferably, the mass content of tar in the waste liquid containing the quaternary ancestral ester is less than or equal to 1000ppm, for example, 1000ppm, 900ppm, 800ppm, 700ppm, 600ppm, 500ppm, 400ppm, 300ppm, 200ppm or 100ppm, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably less than or equal to 500ppm.
Preferably, the neopentyl glycol content in the waste liquid containing the quaternary ancestral ester is less than or equal to 5% by mass, for example, 5%, 4.5%, 4.0%, 3.5%, 3.0%, 2.5%, 2%, 1.5% or 1%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably less than or equal to 3%.
Preferably, the catalyst used for the catalytic decomposition in step (4) is a basic resin catalyst.
Preferably, the basic resin catalyst is obtained by swelling and aminating a styrene-divinylbenzene copolymer.
Preferably, the styrene-divinylbenzene copolymer is a copolymer bead obtained by suspension polymerization of styrene and divinylbenzene.
In the invention, the catalyst prepared by the method further improves the catalytic decomposition effect and the yield of the neopentyl glycol.
Preferably, the molar ratio of styrene to divinylbenzene is (2-5): 1, which may be, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but is not limited to the recited values, as are other non-recited values within the range of values.
Preferably, the styrene-divinylbenzene copolymer has a molecular weight of from 108.5 to 112.8, which may be, for example, 108.5, 112 or 112.8, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the swelling agent used for the swelling comprises toluene.
Preferably, the mass ratio of toluene to styrene-divinylbenzene copolymer is (4-8): 1, which may be, for example, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1 or 8:1, but is not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably (4-6): 1.
Preferably, the swelling time is 6-10h, for example, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h or 10h, but not limited to the recited values, other non-recited values within the range are equally applicable, preferably 6-8h.
Preferably, the swelling temperature is 10-40 ℃, for example, 10 ℃, 15 ℃,20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 15-20 ℃.
Preferably, the amination agent used for the amination comprises tetraethylenepentamine and sodium hydroxide.
Preferably, the mass ratio of tetraethylenepentamine to sodium hydroxide is (1.5-3): 1, for example, it may be 1.5:1, 2:1, 2.5:1 or 3:1, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the mass ratio of tetraethylenepentamine to sodium hydroxide is preferably controlled in a specific range, so that the alkalinity of the catalyst can be further regulated, and the catalytic decomposition effect is improved.
Preferably, the mass ratio of the tetraethylenepentamine to the swollen styrene-divinylbenzene copolymer is (2-5): 1, for example, 2:1, 3:1, 4:1 or 5:1, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the amination temperature is 100-120 ℃, for example, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ or 120 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 110-120 ℃.
Preferably, the amination time is 8-12h, for example, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12h, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 10-12h.
Preferably, the average particle size of the catalyst in step (4) is 0.35-1.25mm, and may be, for example, 0.35mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm, 1.2mm or 1.25mm, but not limited to the values recited, and other non-recited values within the range of values are equally applicable, preferably 0.8-1mm.
In the catalyst, the volume ratio of the catalyst with the particle size smaller than 0.35mm is less than or equal to 5 percent, and the volume ratio of the catalyst with the particle size larger than or equal to 1.25mm is less than or equal to 5 percent.
The invention preferably controls the average particle diameter of the catalyst within a specific range, so that the catalytic decomposition effect can be further improved.
Preferably, the catalyst has a uniformity coefficient of 1.1 to 1.4, which may be, for example, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35 or 1.4, but is not limited to the values recited, and other non-recited values within the range of values are equally applicable, preferably 1.2 to 1.25.
The invention preferably controls the uniformity coefficient of the catalyst in a specific range, and can further improve the catalytic decomposition effect.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Heavy components of the neopentyl glycol product tower are subjected to heavy removal treatment under the conditions that the operating temperature is 155-170 ℃ and the operating pressure is 0.3-1kPaG, so as to obtain a light component gas phase;
the weight percentage of the quaternary ancestral ester in the light component gas phase obtained by the weight removal treatment is 40-45%, and the weight percentage of the neopentyl glycol is 35-45%; the heavy component liquid phase is obtained by the heavy component removal treatment, the heavy component liquid phase contains tar, and the mass of the tar accounts for 10-15% of the mass of heavy components in the neopentyl glycol product tower;
(2) Condensing the light component gas phase obtained in the step (1) to obtain condensate;
(3) Rectifying and recycling the condensate obtained in the step (2) in a recycling tower to obtain a heavy component containing quaternary ancestral ester;
The temperature of the tower bottom of the recovery tower is 185-195 ℃, the operating pressure of the tower top of the recovery tower is 5-8kPaG, the packing of the recovery tower comprises silk screen structured packing, the height of the silk screen structured packing is 10-15m, and the reflux ratio of rectification recovery is 8-15;
The mass percentage of the quaternary ancestral ester in the heavy component containing the quaternary ancestral ester obtained by rectification and recovery is 75-85%; the rectification recovery also obtains a light component containing neopentyl glycol, and the mass percentage of the neopentyl glycol in the light component containing neopentyl glycol obtained by rectification recovery is 95-99%;
(4) Carrying out catalytic decomposition on the heavy component containing the quaternary ancestral ester obtained in the step (3) in a decomposition tower to obtain a neopentyl glycol crude product, returning the neopentyl glycol crude product to the step (1) for heavy removal treatment, and repeating the steps (1) to (3) until the neopentyl glycol crude product is extracted from the light component containing the neopentyl glycol obtained by rectification recovery to obtain a neopentyl glycol product;
The diameter of the decomposing tower is 0.4-0.6m, the decomposing tower is filled with a catalyst, the volume of the catalyst filled in the decomposing tower is 0.2-0.3m 3, and the residence time of the heavy component containing the quaternary ancestral ester in the decomposing tower is 1-1.2h;
The catalyst used for catalytic decomposition is an alkaline resin catalyst, the alkaline resin catalyst is prepared by swelling a styrene-divinylbenzene copolymer at 10-40 ℃ for 6-10h, then aminating the swelled styrene-divinylbenzene copolymer at 100-120 ℃ for 8-12h, the styrene-divinylbenzene copolymer is a copolymer bead body obtained by suspension polymerization of styrene and divinylbenzene, the molar ratio of the styrene to the divinylbenzene is (2-5) 1, the molecular weight of the styrene-divinylbenzene copolymer is 108.5-112.8, the swelling agent used for swelling comprises toluene, the mass ratio of the toluene to the styrene-divinylbenzene copolymer is (4-8) 1, the aminating agent used for amination comprises tetraethylenepentamine and sodium hydroxide, the mass ratio of the tetraethylenepentamine to the sodium hydroxide is (1.5-3), the mass ratio of the tetraethylenepentamine to the swelled styrene-divinylbenzene is (2-5) 1, the average particle size of the catalyst is 0.35-1.25mm, and the mass ratio of the catalyst used for the amination is 1.35-1.25 mm;
Obtaining a neopentyl glycol crude product at the top of the decomposing tower; the waste liquid containing the quaternary ancestral ester is obtained at the tower bottom of the decomposing tower, wherein the mass content of tar is less than or equal to 1000ppm, and the mass content of neopentyl glycol is less than or equal to 5%.
Compared with the prior art, the invention has the following beneficial effects:
The method provided by the invention can utilize the heavy components of the neopentyl glycol product tower, not only recover the neopentyl glycol therein, but also fully decompose and utilize the quaternary ancestral ester therein, further catalyze and decompose the neopentyl glycol into the neopentyl glycol, thereby improving the yield of the neopentyl glycol product, not only having low cost, but also greatly saving energy consumption, the yield of the neopentyl glycol can reach more than 50.5 percent, and the total recovery income can reach more than 505.2 yuan/h.
Drawings
FIG. 1 is a schematic view of a reaction apparatus used in the method of example 1 of the present invention;
FIG. 2 is a schematic view showing the structure of a decomposing column used in embodiment 1 of the present invention;
wherein, 1-scraper evaporator; a 2-condenser; 3-a recovery tower; 4-a decomposing column; 5-a reflux drum; 6-heavy component storage tank.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In a specific embodiment, the method for improving the yield of neopentyl glycol by catalytically decomposing the quaternary ancestral ester is carried out in a reaction device, the structural schematic diagram of the reaction device is shown in fig. 1, the reaction device comprises a scraper evaporator 1, a condenser 2, a recovery tower 3 and a decomposition tower 4 which are sequentially connected, a gas phase outlet of the scraper evaporator 1 is connected with the condenser 2, an outlet of the condenser 2 is connected with the recovery tower 3, a tower bottom liquid phase outlet of the recovery tower 3 is connected with the decomposition tower 4, and the scraper evaporator 1, the condenser 2, the recovery tower 3 and the decomposition tower 4 are matched with each other, so that the recovery of neopentyl glycol, condensation, rectification recovery and catalytic decomposition can be sequentially carried out, thereby improving the yield of neopentyl glycol and reducing the treatment energy consumption and the treatment cost;
The top outlet of the recovery tower 3 is connected with a reflux tank 5, the outlet of the reflux tank 5 is connected with the recovery tower 3, the light components at the top of the recovery tower 3 can flow into the reflux tank 5, part of liquid phase in the reflux tank 5 flows back into the recovery tower 3, and part of liquid phase is extracted to obtain neopentyl glycol products;
The liquid phase outlet of the scraper evaporator 1 is connected with the heavy component storage tank 6, so that the heavy component liquid phase obtained at the bottom of the scraper evaporator 1 can be sent to the heavy component storage tank 6 and then sent to incineration treatment;
The top outlet of the decomposing tower 4 is connected with the scraper evaporator 1, light components generated at the top of the decomposing tower 4 can be condensed and then sent into the scraper evaporator 1, waste liquid at the bottom of the decomposing tower is sent to the waste liquid for incineration, the operation from the step (1) to the step (3) is repeated until neopentyl glycol-containing light components obtained by rectification recovery are extracted, a neopentyl glycol product is obtained, and the neopentyl glycol product is sent into a product tower.
Example 1
The embodiment provides a method for improving the yield of neopentyl glycol by catalytically decomposing quaternary ancestral ester, wherein the structural schematic diagram of a reaction device is shown in fig. 1, the device comprises a scraper evaporator 1, a condenser 2, a recovery tower 3, a reflux tank 5, a decomposing tower 4 and a heavy component storage tank 6, and the method comprises the following steps:
(1) Feeding heavy components of a neopentyl glycol product tower (containing 40.0% of neopentyl glycol, 38.0% of quaternary ancestral ester and 9.8% of tar by mass percent) into a scraper evaporator 1, carrying out heavy removal treatment under the condition that the operating temperature is 161 ℃ and the operating pressure is 0.5kPaG, obtaining a light component gas phase at the top of the scraper evaporator 1, obtaining a heavy component liquid phase at the bottom of the scraper evaporator 1, feeding the heavy component liquid phase into a heavy component storage tank 6, and then feeding the heavy component liquid phase into incineration treatment;
(2) Sending the light component gas phase obtained in the step (1) into a condenser 2 for condensation, wherein the condensation temperature is 100 ℃, and the condenser 2 adopts a tube array vertical heat exchanger to obtain condensate;
(3) Feeding the condensate obtained in the step (2) into a recovery tower 3, rectifying and recovering the condensate in the recovery tower 3, obtaining heavy components containing quaternary ancestral esters at the tower bottom of the recovery tower 3, obtaining light components containing neopentyl glycol at the tower top of the recovery tower 3, condensing the light components containing neopentyl glycol, then feeding the light components into a reflux tank 5, refluxing a part of liquid phase in the reflux tank 5 to the recovery tower 3, and extracting a part of liquid phase to obtain neopentyl glycol products;
The temperature of the tower bottom of the recovery tower 3 is 189 ℃, the operation pressure of the tower top of the recovery tower 3 is 7kPaG, the packing of the recovery tower 3 is plate ripple silk screen structured packing, the height is 10m, and the reflux ratio of rectification recovery is 10;
(4) Feeding the recombinant product containing the quaternary ancestral ester obtained in the step (3) into a decomposing tower 4, carrying out catalytic decomposition in the decomposing tower 4, obtaining waste liquid containing the quaternary ancestral ester at the tower bottom of the decomposing tower 4, sending the waste liquid to burn, obtaining a neopentyl glycol crude product at the tower top of the decomposing tower 4, returning the neopentyl glycol crude product to the scraper evaporator 1 in the step (1), repeating the operations from the step (1) to the step (3) along with the heavy component of the neopentyl glycol product tower, and finally extracting the neopentyl glycol product from a reflux tank 5, wherein the neopentyl glycol product is returned to the product tower in the step (1) for further purification;
The schematic structural diagram of the decomposing tower 4 is shown in fig. 2, the tower diameter of the decomposing tower 4 is 0.5m, the decomposing tower 4 is filled with catalyst, the volume of the catalyst filled in the decomposing tower 4 is 0.2m 3, and the residence time of the heavy component containing the quaternary ancestral ester in the decomposing tower 4 is 1.2h;
The catalyst used in the catalytic decomposition is an alkaline resin catalyst, the alkaline resin catalyst is prepared by swelling a styrene-divinylbenzene copolymer with toluene at 20 ℃ for 6 hours, then aminating the swelled styrene-divinylbenzene copolymer with tetraethylenepentamine and sodium hydroxide at 120 ℃ for 10 hours, the styrene-divinylbenzene copolymer is a copolymer bead body obtained by suspension polymerization of styrene and divinylbenzene, the molar ratio of the styrene to the divinylbenzene is 2:1, the molecular weight of the styrene-divinylbenzene copolymer is 112, the mass ratio of the toluene to the styrene-divinylbenzene copolymer is 5:1, the mass ratio of the tetraethylenepentamine to the sodium hydroxide is 2:1, the mass ratio of the tetraethylenepentamine to the swelled styrene-divinylbenzene copolymer is 4:1, the average particle size of the catalyst is 0.8mm, and the uniformity coefficient of the catalyst is 1.2;
In this example, the amount of the steam 20S consumed by the wiped evaporator 1 was 0.18 ton/h, the amount of the steam 20S consumed by the recovery tower 3 was 0.25 ton/h, and the amount of the 2S steam generated at the top of the tower was 0.15t/h.
Example 2
This example provides a process for the catalytic decomposition of a quaternary ancestral ester to increase the yield of neopentyl glycol using the same reaction apparatus as in example 1, comprising the steps of:
(1) Feeding heavy components of a neopentyl glycol product tower (containing 35.0% of neopentyl glycol, 38.0% of quaternary ancestral ester and 12% of tar) into a scraper evaporator, carrying out heavy removal treatment under the conditions of the operating temperature of 165 ℃ and the operating pressure of 1kPaG, obtaining a light component gas phase at the top of the scraper evaporator, obtaining a heavy component liquid phase at the bottom of the scraper evaporator, feeding the heavy component liquid phase into a heavy component storage tank, and then feeding into an incineration treatment;
(2) Sending the light component gas phase obtained in the step (1) into a condenser for condensation, wherein the condensation temperature is 100 ℃, and the condenser adopts a tube array vertical heat exchanger to obtain condensate;
(3) Feeding the condensate obtained in the step (2) into a recovery tower, rectifying and recovering the condensate in the recovery tower, obtaining heavy components containing quaternary first-class esters at the tower bottom of the recovery tower, obtaining light components containing neopentyl glycol at the tower top of the recovery tower, condensing the light components containing neopentyl glycol, then feeding the light components into a reflux tank, and refluxing a part of liquid phase in the reflux tank to the recovery tower, and extracting a part of liquid phase to obtain a neopentyl glycol product;
The temperature of the tower bottom of the recovery tower is 190 ℃, the operating pressure of the tower top of the recovery tower is 7kPaG, the packing of the recovery tower is plate ripple silk screen structured packing, the height is 10m, and the reflux ratio of rectification recovery is 10;
(4) Feeding the recombinant product containing the quaternary ancestral ester obtained in the step (3) into a decomposition tower, carrying out catalytic decomposition in the decomposition tower, obtaining waste liquid containing the quaternary ancestral ester at the tower bottom of the decomposition tower, feeding the waste liquid to burn, obtaining a neopentyl glycol crude product at the tower top of the decomposition tower, returning the neopentyl glycol crude product to the scraper evaporator in the step (1), repeating the operations from the step (1) to the step (3) along with the heavy component of the neopentyl glycol product tower, and finally extracting the neopentyl glycol product from a reflux tank, wherein the neopentyl glycol product is returned to the product tower in the step (1) for further purification;
The diameter of the decomposing tower is 0.5m, the decomposing tower is filled with a catalyst, the volume of the catalyst in the decomposing tower is 0.2m 3, and the residence time of the heavy component containing the quaternary ancestral ester in the decomposing tower is 1.2h;
The catalyst used in the catalytic decomposition is an alkaline resin catalyst, the alkaline resin catalyst is prepared by swelling a styrene-divinylbenzene copolymer with toluene at 20 ℃ for 6 hours, then aminating the swelled styrene-divinylbenzene copolymer with tetraethylenepentamine and sodium hydroxide at 120 ℃ for 10 hours, the styrene-divinylbenzene copolymer is a copolymer bead body obtained by suspension polymerization of styrene and divinylbenzene, the molar ratio of the styrene to the divinylbenzene is 2:1, the molecular weight of the styrene-divinylbenzene copolymer is 112, the mass ratio of the toluene to the styrene-divinylbenzene copolymer is 5:1, the mass ratio of the tetraethylenepentamine to the sodium hydroxide is 2:1, the mass ratio of the tetraethylenepentamine to the swelled styrene-divinylbenzene copolymer is 4:1, the average particle size of the catalyst is 0.8mm, and the uniformity coefficient of the catalyst is 1.2;
In this example, the amount of the wiped evaporator consumed the steam 20S was 0.2 ton/h, the amount of the recovery column consumed the steam 20S was 0.28 ton/h, and the amount of the overhead 2S steam was 0.16t/h.
Example 3
This example provides a process for the catalytic decomposition of a quaternary ancestral ester to increase the yield of neopentyl glycol using the same reaction apparatus as in example 1, comprising the steps of:
(1) Feeding heavy components of a neopentyl glycol product tower (containing 41.0% of neopentyl glycol, 38.0% of quaternary ancestral ester, 3835.5% of Jiao Youlei% of quaternary ancestral ester and the balance of impurities in percentage by mass) into a scraper evaporator, carrying out heavy removal treatment under the conditions of an operating temperature of 161 ℃ and an operating pressure of 0.5kPaG, obtaining a light component gas phase at the top of the scraper evaporator, obtaining a heavy component liquid phase at the bottom of the scraper evaporator, feeding the heavy component liquid phase into a heavy component storage tank, and then feeding the heavy component liquid phase into an incineration treatment;
(2) Sending the light component gas phase obtained in the step (1) into a condenser for condensation, wherein the condensation temperature is 100 ℃, and the condenser adopts a tube array vertical heat exchanger to obtain condensate;
(3) Feeding the condensate obtained in the step (2) into a recovery tower, rectifying and recovering the condensate in the recovery tower, obtaining heavy components containing quaternary first-class esters at the tower bottom of the recovery tower, obtaining light components containing neopentyl glycol at the tower top of the recovery tower, condensing the light components containing neopentyl glycol, then feeding the light components into a reflux tank, and refluxing a part of liquid phase in the reflux tank to the recovery tower, and extracting a part of liquid phase to obtain a neopentyl glycol product;
the temperature of the tower bottom of the recovery tower is 179 ℃, the operation pressure of the tower top of the recovery tower is 8kPaG, the packing of the recovery tower is plate ripple silk screen structured packing, the height is 10m, and the reflux ratio of rectification recovery is 8;
(4) Feeding the recombinant product containing the quaternary ancestral ester obtained in the step (3) into a decomposition tower, carrying out catalytic decomposition in the decomposition tower, obtaining waste liquid containing the quaternary ancestral ester at the tower bottom of the decomposition tower, feeding the waste liquid to burn, obtaining a neopentyl glycol crude product at the tower top of the decomposition tower, returning the neopentyl glycol crude product to the scraper evaporator in the step (1), repeating the operations from the step (1) to the step (3) along with the heavy component of the neopentyl glycol product tower, and finally extracting the neopentyl glycol product from a reflux tank, wherein the neopentyl glycol product is returned to the product tower in the step (1) for further purification;
The diameter of the decomposing tower is 0.5m, the decomposing tower is filled with a catalyst, the volume of the catalyst in the decomposing tower is 0.2m 3, and the residence time of the heavy component containing the quaternary ancestral ester in the decomposing tower is 1.2h;
The catalyst used in the catalytic decomposition is an alkaline resin catalyst, the alkaline resin catalyst is prepared by swelling a styrene-divinylbenzene copolymer with toluene at 20 ℃ for 6 hours, then aminating the swelled styrene-divinylbenzene copolymer with tetraethylenepentamine and sodium hydroxide at 120 ℃ for 10 hours, the styrene-divinylbenzene copolymer is a copolymer bead body obtained by suspension polymerization of styrene and divinylbenzene, the molar ratio of the styrene to the divinylbenzene is 5:1, the molecular weight of the styrene-divinylbenzene copolymer is 108.5, the mass ratio of the toluene to the styrene-divinylbenzene copolymer is 5:1, the mass ratio of the tetraethylenepentamine to the sodium hydroxide is 2:1, the mass ratio of the tetraethylenepentamine to the swelled styrene-divinylbenzene copolymer is 4:1, the average particle size of the catalyst is 0.8mm, and the uniformity coefficient of the catalyst is 1.2;
In this example, the amount of the wiped evaporator consumed the steam 20S was 0.18 ton/h, the amount of the recovery column consumed the steam 20S was 0.23 ton/h, and the amount of the overhead 2S steam was 0.14t/h.
Example 4
This example provides a method for improving neopentyl glycol yield by catalytic decomposition of quaternary ancestral esters, which differs from example 1 only in that the operating temperature of the de-duplication treatment is 140 ℃.
Example 5
This example provides a process for the catalytic decomposition of quaternary ancestral esters to increase the neopentyl glycol yield, differing from example 1 only in the 180℃operating temperature of the stripping treatment.
Example 6
This example provides a method for improving neopentyl glycol yield by catalytic decomposition of quaternary ancestral ester, which differs from example 1 only in that the temperature of the recovery column bottoms is 160 ℃.
Example 7
This example provides a method for improving neopentyl glycol yield by catalytic decomposition of quaternary ancestral ester, which differs from example 1 only in that the temperature of the recovery column bottom is 200 ℃.
Example 8
This example provides a process for the catalytic decomposition of quaternary ancestral esters to increase the neopentyl glycol yield, differing from example 1 only in the residence time in the decomposition column of 0.5h.
Example 9
This example provides a process for the catalytic decomposition of quaternary ancestral esters to increase the neopentyl glycol yield, differing from example 1 only in the residence time in the decomposition column of 2h.
Example 10
This example provides a method for improving neopentyl glycol yield by catalytic decomposition of quaternary ancestral esters, which differs from example 1 only in that the mass ratio of tetraethylenepentamine to sodium hydroxide is 1:1.
Example 11
This example provides a method for improving neopentyl glycol yield by catalytic decomposition of quaternary ancestral esters, which differs from example 1 only in that the mass ratio of tetraethylenepentamine to sodium hydroxide is 4:1.
Example 12
This example provides a method for catalytically decomposing a quaternary ancestral ester to increase neopentyl glycol yield, differing from example 1 only in the replacement of the catalyst with the catalyst of CN112142565A example 1.
Comparative example 1
This comparative example provides a method for recovering neopentyl glycol, which is different from example 1 only in that step (4) is not performed, namely, the heavy component of the quaternary ancestral ester recovered by rectification is directly used as waste liquid for incineration treatment, and the light component containing neopentyl glycol recovered by rectification is pumped to a neopentyl glycol product tower in the original flow after being condensed.
The neopentyl glycol product column used in this comparative example contained, by mass, 39.0% neopentyl glycol, 38.0% quaternary ancestral ester and 9.5% tar.
In this comparative example, the amount of the wiped evaporator consumed the steam 20S was 0.18 ton/h, the amount of the recovery column consumed the steam 20S was 0.23 ton/h, and the amount of the overhead 2S steam was 0.12t/h.
Taking examples 1-3 and comparative example 1 as examples, the mass percentages of neopentyl glycol, the quaternary ancestral ester and the tar contained in the feed in step (1), the condensed liquid in step (2), the bottom of the recovery column in step (3) and the top of the decomposition column in step (4) were measured, and the results are shown in Table 1.
The energy consumption costs in examples 1 to 3 and comparative example 1 were calculated using examples 1 to 3 and comparative example 1, and the results are shown in Table 2. Wherein the 2S cost unit price is 43.44 yuan/ton; the cost unit price of 20S is 136 yuan/ton; the recovery cost unit price of the neopentyl glycol is 10000 yuan/ton; the cost of waste liquid incineration is 270 yuan/ton.
The yields and total recovery yields of neopentyl glycol in examples 1 to 12 and comparative example 1 were calculated, and the results are shown in Table 3.
TABLE 1
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TABLE 2
TABLE 3 Table 3
| Neopentyl glycol yield/% | Total recovery yield/(yuan/h) | |
| Example 1 | 71.1 | 736.1 |
| Example 2 | 61.9 | 641.2 |
| Example 3 | 69.8 | 722.2 |
| Example 4 | 55.4 | 573.6 |
| Example 5 | 60.5 | 626.4 |
| Example 6 | 57.8 | 598.4 |
| Example 7 | 60.5 | 626.4 |
| Example 8 | 60.1 | 622.2 |
| Example 9 | 60.5 | 626.4 |
| Example 10 | 50.5 | 522.8 |
| Example 11 | 48.8 | 505.2 |
| Example 12 | 52.1 | 539.4 |
| Comparative example 1 | 37.9 | 482 |
From tables 1-3, the following points can be seen:
(1) As can be seen from tables 1-3, the method provided by the invention can recover heavy components in the feed, and the generated neopentyl glycol is concentrated at the top of the decomposing tower, so that the yield of the neopentyl glycol is more than 50.5%, the energy consumption cost can be reduced, and the total recovery income is more than 505.2 yuan/h.
(2) As can be seen from a combination of the data of examples 1 and examples 4 to 5, the operating temperature of the de-duplication treatment in example 1 was 161 c, and the yield and total recovery yield of neopentyl glycol in example 1 were significantly higher than those of examples 4 to 5 compared to 140 c and 180 c, respectively, and it can be seen that the present invention preferably controls the operating temperature of the de-duplication treatment, and further improves the yield of neopentyl glycol and reduces the energy consumption.
(3) As can be seen from a combination of the data of examples 1 and examples 6 to 7, the recovery column bottoms of example 1 had a temperature of 189 c, and the yield and total recovery yield of neopentyl glycol of example 1 were significantly higher than those of examples 6 to 7, compared to 160 c and 200 c, respectively, and thus, it can be seen that the present invention preferably controls the recovery column bottoms temperature, thereby further improving the yield of neopentyl glycol and reducing the energy consumption.
(4) As can be seen from a combination of the data in examples 1 and examples 8 to 9, the residence time in the decomposition column in example 1 was 1.2h, and the yield and total recovery yield of neopentyl glycol in example 1 were significantly higher than those in examples 8 to 9, compared to 0.5h and 2h in examples 8 to 9, respectively, whereby it can be seen that the present invention preferably controls the residence time in the decomposition column, and further improves the yield of neopentyl glycol and reduces the energy consumption.
(5) As can be seen from a combination of the data of examples 1 and examples 10 to 12, the mass ratio of tetraethylenepentamine to sodium hydroxide in the catalyst obtained in example 1 was 4:1, and the yield and total recovery yield of neopentyl glycol in example 1 were significantly higher than those of examples 10 to 12 compared to the catalysts used in examples 10 to 11 of 1:1 and 4:1, respectively, and thus, it was found that the present invention preferably used a specific catalyst and controlled mass ratio of tetraethylenepentamine to sodium hydroxide, and further improved the yield of neopentyl glycol and reduced the energy consumption.
(6) From a combination of the data of comparative example 1 and comparative example 1, it can be seen that comparative example 1 differs from example 1 only in that step (4) is not performed, and the yield and total recovery yield of neopentyl glycol in example 1 are significantly higher than those of comparative example 1, whereby it can be seen that the process of the present invention can greatly improve the yield of neopentyl glycol and reduce the energy consumption.
In summary, the method provided by the invention can utilize the heavy components of the neopentyl glycol product tower, so that not only is the neopentyl glycol recovered, but also the yield of the neopentyl glycol is improved, and the energy consumption is reduced.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (52)
1. A method for improving neopentyl glycol yield by catalytically decomposing a quaternary ancestral ester, comprising the steps of:
(1) Heavy component removal treatment is carried out on heavy component in a tower for preparing neopentyl glycol products by a condensation hydrogenation method, and a light component gas phase is obtained;
The weight removing treatment in the step (1) is carried out in a scraper evaporator;
(2) Condensing the light component gas phase obtained in the step (1) to obtain condensate;
(3) Rectifying and recycling the condensate obtained in the step (2) to obtain a heavy component containing quaternary ancestral ester;
(4) Carrying out catalytic decomposition on the heavy component containing the quaternary ancestral ester obtained in the step (3) to obtain a neopentyl glycol crude product;
The catalyst used for the catalytic decomposition in the step (4) is an alkaline resin catalyst;
The alkaline resin catalyst in the step (4) is obtained by swelling and aminating a styrene-divinylbenzene copolymer;
The styrene-divinylbenzene copolymer in the step (4) is a copolymer bead body obtained by suspension polymerization of styrene and divinylbenzene;
The swelling agent used in the swelling in the step (4) is toluene;
The swelling time in the step (4) is 6-10h; the swelling temperature is 10-40 ℃;
the amination agent used in the amination in the step (4) is tetraethylenepentamine and sodium hydroxide;
The amination temperature in the step (4) is 100-120 ℃; the amination time is 8-12h.
2. The method of claim 1, wherein the de-duplication treatment is operated at a temperature of 155-170 ℃.
3. The method according to claim 2, wherein the de-duplication treatment is operated at a temperature of 160-165 ℃.
4. The method of claim 1, wherein the operating temperature of the de-duplication treatment is at an operating pressure of 0.3 to 1kPaG.
5. The method of claim 4, wherein the operating temperature of the de-duplication treatment is at an operating pressure of 0.3 to 0.5kPaG.
6. The method according to claim 1, wherein the weight percentage of the quaternary ancestral ester in the light component gas phase obtained by the weight removal treatment in the step (1) is 40-45%.
7. The process according to claim 1, wherein the weight percentage of neopentyl glycol in the light component gas phase obtained by the weight removal treatment in step (1) is from 35 to 45%.
8. The process of claim 1 wherein the de-duplication treatment of step (1) also results in a heavy component liquid phase.
9. The method of claim 8, wherein the heavy ends liquid phase comprises tar.
10. The method of claim 9, wherein the tar comprises 10-15% of the mass of the heavy component of the neopentyl glycol product column.
11. The method according to claim 1, wherein the mass percentage of quaternary ancestral ester in the quaternary ancestral ester-containing heavy component recovered by the rectification in the step (3) is 75-85%.
12. The process of claim 1 wherein said rectifying recovery of step (3) further yields a light component comprising neopentyl glycol.
13. The method according to claim 12, wherein the neopentyl glycol is recovered as a light component containing neopentyl glycol by distillation in an amount of 95 to 99% by mass.
14. The process of claim 12 wherein a portion of the light neopentyl glycol-containing component is refluxed and a portion of the neopentyl glycol-containing component is recovered to yield a neopentyl glycol product.
15. The method of claim 1, wherein the rectifying recovery of step (3) is performed in a recovery column.
16. The method of claim 15, wherein the recovery column bottoms temperature is 185-195 ℃.
17. The method of claim 16, wherein the recovery column bottoms temperature is 185-190 ℃.
18. The process of claim 15 wherein the recovery column overhead operating pressure is from 5 to 8kPaG.
19. The process of claim 18 wherein the recovery column overhead operating pressure is from 6 to 8kPaG.
20. The method of claim 15, wherein the packing of the recovery column is a wire mesh structured packing.
21. The method of claim 20, wherein the height of the wire mesh structured packing is 10-15m.
22. The method of claim 21, wherein the height of the wire mesh structured packing is 10-12m.
23. The method of claim 15, wherein the reflux ratio recovered by the rectification is from 8 to 15.
24. The method of claim 23, wherein the reflux ratio recovered by the rectification is from 10 to 12.
25. The method of claim 1, wherein the catalytic decomposition in step (4) is at a temperature of 80-90 ℃.
26. The method according to claim 1, wherein the catalytic decomposition of step (4) is performed in a decomposition column.
27. The method of claim 26, wherein the decomposing column has a column diameter of 0.4 to 0.6m.
28. The method of claim 27, wherein the decomposition column is packed with catalyst.
29. The method of claim 28, wherein the decomposing column is filled with catalyst in a volume of 0.2-0.3m 3.
30. The method of claim 26, wherein the residence time of the quaternary ancestral ester-containing heavies in the decomposition column is from 1 to 1.2 hours.
31. The process of claim 26, wherein the top of the decomposition column gives a crude neopentyl glycol product.
32. The process of claim 31 wherein the crude neopentyl glycol product is returned to the de-duplication of step (1).
33. The method of claim 26, wherein the bottoms of the decomposing column yields a waste stream comprising quaternary ancestral esters.
34. The method of claim 33, wherein the mass content of tar in the waste liquor containing quaternary ancestral esters is less than or equal to 1000ppm.
35. The method of claim 34, wherein the mass content of tar in the waste liquor containing quaternary ancestral esters is less than or equal to 500ppm.
36. The method of claim 33, wherein the neopentyl glycol is present in an amount of less than or equal to 5% by mass of the waste liquor containing the quaternary ancestral ester.
37. The method of claim 36, wherein the neopentyl glycol is present in the waste liquor comprising the quaternary ancestral ester in a mass percentage of 3% or less.
38. The method of claim 1, wherein the molar ratio of styrene to divinylbenzene is (2-5): 1.
39. The method of claim 1, wherein the styrene-divinylbenzene copolymer has a molecular weight of from 108.5 to 112.8.
40. The process according to claim 1, wherein the mass ratio of toluene to styrene-divinylbenzene copolymer is (4-8): 1.
41. The process of claim 40 wherein the mass ratio of toluene to styrene-divinylbenzene copolymer is from (4 to 6): 1.
42. The method of claim 1, wherein the swelling time is from 6 to 8 hours.
43. The method of claim 1, wherein the swelling temperature is 15-20 ℃.
44. The method according to claim 1, wherein the mass ratio of tetraethylenepentamine to sodium hydroxide is (1.5-3): 1.
45. The method according to claim 1, wherein the mass ratio of tetraethylenepentamine to the swollen styrene-divinylbenzene copolymer is (2-5): 1.
46. The method of claim 1, wherein the amination is at a temperature of 110-120 ℃.
47. The method of claim 1, wherein the amination is for a period of 10 to 12 hours.
48. The process of claim 1, wherein the catalyst of step (4) has an average particle size of 0.35 to 1.25mm.
49. The process of claim 48 wherein the average particle size of the catalyst in step (4) is from 0.8 to 1mm.
50. The method of claim 1, wherein the catalyst of step (4) has a uniformity factor of 1.1 to 1.4.
51. The method of claim 50, wherein the catalyst of step (4) has a uniformity factor of 1.2 to 1.25.
52. The method according to claim 1, characterized in that it comprises the steps of:
(1) Heavy components of the neopentyl glycol product tower are subjected to heavy removal treatment under the conditions that the operating temperature is 155-170 ℃ and the operating pressure is 0.3-1kPaG, so as to obtain a light component gas phase;
the weight percentage of the quaternary ancestral ester in the light component gas phase obtained by the weight removal treatment is 40-45%, and the weight percentage of the neopentyl glycol is 35-45%; the heavy component liquid phase is obtained by the heavy component removal treatment, the heavy component liquid phase contains tar, and the mass of the tar accounts for 10-15% of the mass of heavy components in the neopentyl glycol product tower;
(2) Condensing the light component gas phase obtained in the step (1) to obtain condensate;
(3) Rectifying and recycling the condensate obtained in the step (2) in a recycling tower to obtain a heavy component containing quaternary ancestral ester;
The temperature of the tower bottom of the recovery tower is 185-195 ℃, the operating pressure of the tower top of the recovery tower is 5-8kPaG, the filler of the recovery tower is silk screen structured filler, the height of the silk screen structured filler is 10-15m, and the reflux ratio of rectification recovery is 8-15;
The mass percentage of the quaternary ancestral ester in the heavy component of the quaternary ancestral ester recovered by rectification is 75-85%; the rectification recovery also obtains a light component containing neopentyl glycol, and the mass percentage of the neopentyl glycol in the light component containing neopentyl glycol obtained by rectification recovery is 95-99%;
(4) Carrying out catalytic decomposition on the heavy component containing the quaternary ancestral ester obtained in the step (3) in a decomposition tower to obtain a neopentyl glycol crude product, returning the neopentyl glycol crude product to the heavy removal treatment in the step (1), and repeating the steps (1) to (3) until the neopentyl glycol crude product is extracted from the light component containing the neopentyl glycol obtained by rectification recovery to obtain a neopentyl glycol product;
The diameter of the decomposing tower is 0.4-0.6m, the decomposing tower is filled with a catalyst, the volume of the catalyst filled in the decomposing tower is 0.2-0.3m 3, and the residence time of the heavy component containing the quaternary ancestral ester in the decomposing tower is 1-1.2h;
The catalyst used for catalytic decomposition is an alkaline resin catalyst, the alkaline resin catalyst is prepared by swelling a styrene-divinylbenzene copolymer at 10-40 ℃ for 6-10h, then aminating the swelled styrene-divinylbenzene copolymer at 100-120 ℃ for 8-12h, the styrene-divinylbenzene copolymer is a copolymer bead body obtained by suspension polymerization of styrene and divinylbenzene, the molar ratio of the styrene to the divinylbenzene is (2-5) 1, the molecular weight of the styrene-divinylbenzene copolymer is 108.5-112.8, the swelling agent used for swelling comprises toluene, the mass ratio of the toluene to the styrene-divinylbenzene copolymer is (4-8) 1, the aminating agent used for amination comprises tetraethylenepentamine and sodium hydroxide, the mass ratio of the tetraethylenepentamine to the sodium hydroxide is (1.5-3), the mass ratio of the tetraethylenepentamine to the swelled styrene-divinylbenzene is (2-5) 1, the average particle size of the catalyst is 0.35-1.25mm, and the mass ratio of the catalyst used for the amination is 1.35-1.25 mm;
Obtaining a neopentyl glycol crude product at the top of the decomposing tower; the waste liquid containing the quaternary ancestral ester is obtained at the tower bottom of the decomposing tower, wherein the mass content of tar is less than or equal to 1000ppm, and the mass content of neopentyl glycol is less than or equal to 5%.
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