CN110003138B - Method for removing aldehyde and ketone in HPPO (high pressure propylene oxide) process by using molecular sieve catalytic reaction - Google Patents
Method for removing aldehyde and ketone in HPPO (high pressure propylene oxide) process by using molecular sieve catalytic reaction Download PDFInfo
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- CN110003138B CN110003138B CN201910342601.3A CN201910342601A CN110003138B CN 110003138 B CN110003138 B CN 110003138B CN 201910342601 A CN201910342601 A CN 201910342601A CN 110003138 B CN110003138 B CN 110003138B
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- 238000000034 method Methods 0.000 title claims abstract description 64
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 150000002576 ketones Chemical class 0.000 title claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 150000001299 aldehydes Chemical class 0.000 title claims description 44
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000012535 impurity Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- -1 aldehyde ketone Chemical class 0.000 claims abstract description 26
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 claims abstract 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7003—A-type
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a method for removing aldehyde ketone in circulating methanol in an HPPO (propylene glycol ether peroxide) process by using a molecular sieve catalytic reaction, which is characterized in that a molecular sieve is modified by an ion exchange method, circulating methanol containing aldehyde ketone impurities in the HPPO process is pumped into a fixed bed reaction device filled with a modified molecular sieve at a certain airspeed, and the modified molecular sieve catalyzes aldehyde ketone to react with methanol at a certain temperature and pressure to generate corresponding acetal and ketal, so that purified circulating methanol from which the aldehyde ketone impurities are removed is obtained. The process for removing the aldehyde and ketone impurities is simple, no nitrogen-containing wastewater is generated, and the modified molecular sieve catalyst can be regenerated by simple high-temperature roasting.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a method for removing aldehyde and ketone in an HPPO (HPPO) process by using a molecular sieve catalytic reaction, which is mainly used for treating circulating methanol containing 50-5000ppm aldehyde and ketone impurities.
Background
Propylene Oxide (PO) is the second largest Propylene derivative next to polypropylene, and is an important bulk organic chemical raw material, and is listed in the 50 chemicals with the largest global yield. The propylene oxide is mainly used for producing polyether polyol to further produce polyurethane, and is applied to the fields of coatings, automobiles, buildings, household appliances, transportation and the like. The main production processes for propylene oxide are the chlorohydrin process, the co-oxidation process and the direct oxidation process (HPPO). The chlorohydrination method has serious equipment corrosion and high energy consumption, generates a large amount of waste water and waste residue with high chloride content in the production process, and is difficult to treat. The co-oxidation method has long process flow, large equipment investment and more co-products, and is limited by the raw material source and the market of the co-products. The HPPO method is a method for directly oxidizing propylene into propylene oxide by hydrogen peroxide under the action of a catalyst, has mild conditions, simple process, good product selectivity and less three wastes, and is considered to be the most promising method in the propylene oxide synthesis technology. The HPPO method inevitably generates aldehyde and ketone impurities (formaldehyde, acetaldehyde, propionaldehyde, acetone and the like) in the production process, the boiling points of the impurities are close to that of propylene oxide, the impurities are difficult to separate by common rectification, the quality of the propylene oxide product is poor, and the application of the propylene oxide product in polyurethane is seriously influenced, so that the removal of the aldehyde and ketone impurities becomes one of the key factors influencing the success or failure of the HPPO method.
Multistage rectification is a conventional method for removing aldehyde and ketone impurities in the HPPO process, but the method has the advantages of high energy consumption, low efficiency, high separation loss and high production cost, and is difficult to realize industrialization. Patent CN01804651.7 discloses a method for refining propylene oxide product by using polar solvent such as water for extractive distillation, but aldehyde and ketone impurities cannot be effectively removed. Patent CN200380103986.5 discloses a method for extractive distillation of propylene oxide by using a compound containing unsubstituted amine groups, which can effectively remove aldehyde impurities in the product, but hydrazone products generated by the compound and aldehyde generate high nitrogen-containing wastewater which is difficult to treat. Patent CN201180017377.2 discloses a method for removing aldehyde in propylene oxide by using amine functional resin, patent CN201110434173.0 discloses a method for removing aldehyde ketone by using alkaline resin, patent CN201610115263.6 discloses a method for removing aldehyde impurities by using resin and ethanolamine/hydrazine hydrate combination, but propylene oxide has a certain swelling effect on high polymer resin, so that the problems of high propylene oxide loss, resin strength reduction and breakage are caused. Patent CN201610473450.1 discloses a method for adsorbing propylene oxide aldehyde impurities by using a modified molecular sieve, which overcomes the problem of resin swelling, but is affected by the adsorption efficiency of the molecular sieve, and the regeneration is frequent.
In the circulating solvent methanol of the HPPO method, aldehyde and ketone impurities also need to be removed, so that the quality reduction of products caused by enrichment is avoided. The patents CN03809959.4, CN201410108264.9 and CN201610706066.1 all adopt a method for reducing aldehyde and ketone by adopting a hydrogenation process, and the hydrogenation process is listed in the first major supervision hazardous chemical process, so that the safety control requirement is high and the operation cost is high.
GB/T14491 and 2015 industrial propylene oxide clearly requires the aldehyde impurities (qualified products are less than or equal to 200ppm, superior products are less than or equal to 50ppm), and even requires less than or equal to 10ppm in a few high-end applications. In industrial production, the aldehyde ketone impurities in the circulating methanol are often as high as 100-2000ppm, and the impurities in the circulating methanol must be effectively removed to ensure the product quality. In the prior art, methods for removing aldehyde and ketone impurities are usually adopted, such as amine-containing organic matters, adsorption, hydrogenation and the like, but the problems of difficult wastewater treatment, frequent regeneration, high safety requirement and the like exist. Therefore, the development of a method for efficiently, conveniently and environmentally removing the aldehyde and ketone impurities in the circulating methanol in the HPPO process has important value.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a method for efficiently, conveniently and environmentally removing aldehyde and ketone impurities in circulating methanol of an HPPO process, and relates to a method for catalyzing the aldehyde and ketone impurities to perform a condensation reaction with methanol by using a molecular sieve to remove the aldehyde and ketone impurities in the circulating methanol. The reaction equation involved is as follows:
the invention provides a method for removing aldehyde ketone in circulating methanol by an HPPO process through a molecular sieve catalytic reaction, which comprises the following steps:
(1) preparing a modified molecular sieve: the molecular sieve is one or more of ZSM-5, NaY, A, MCM and Beta molecular sieve, the modification method is an ion exchange method, and the modification reagent is Sn2+、Zn2+、Ca2+、Ni2+、NH4 +、Ti4+、Ag+、Co2+And the like, hydrochloride or nitrate.
(2) Pumping circulating methanol containing aldehyde ketone impurities from an HPPO process into a fixed bed reaction device filled with a modified molecular sieve at a certain airspeed, and catalyzing aldehyde ketone and methanol to react by using the modified molecular sieve at a certain temperature and under a certain pressure to generate corresponding acetal and ketal so as to obtain purified circulating methanol from which the aldehyde ketone impurities are removed;
(3) and (3) after the fixed bed device is operated until the content of the aldehyde and ketone impurities is increased to a certain index, roasting and regenerating the modified molecular sieve in the regeneration gas, and recovering the catalytic activity.
In the step (1), the liquid/solid weight ratio of the ion exchange is 1-5, the temperature is 20-100 ℃, the time is 0.1-10 h/time, the roasting temperature is 300-.
In the step (2), the aldehyde and ketone-containing impurities in the circulating methanol comprise one or more of formaldehyde, acetaldehyde, propionaldehyde, acetone and the like, and the total aldehyde and ketone content is 50-5000 ppm.
In the step (2), the fixed bed reaction device is a traditional tube array type fixed bed, the length-diameter ratio of a single tube array is 10-100, the circulating methanol pumping mode is an up-in-down-out mode or a down-in-up-out mode, and the volume space velocity is 0.1-10h-1。
In the step (2), the temperature of the circulating methanol in the fixed bed reaction device is 40-80 ℃, and the pressure is 0.5-5 Mpa.
In the step (3), the regeneration process is to purge the catalyst to be treated with nitrogen at 400 ℃ under 300-.
Compared with the prior art, the invention has the following advantages:
(1) the process for removing the aldehyde and ketone impurities is simple, and does not generate nitrogen-containing wastewater: the inorganic molecular sieve with stable chemical structure is adopted to replace amine additives or organic polymer resin in the traditional process, thereby fundamentally avoiding the nitrogen-containing wastewater which is difficult to treat.
(2) The molecular sieve has the advantages of simple modification process, long service life, easy regeneration and good economical efficiency: a commercial molecular sieve can be selected, the molecular sieve is modified by adopting an ion exchange method, the surface acidity of the molecular sieve is adjusted, and the catalytic effect on acetal and ketal reaction is enhanced; the catalytic reaction is adopted to replace the adsorption method in the prior art, the efficiency of removing aldehyde and ketone impurities is greatly improved, and the one-way service life of the catalyst is long; the modified molecular sieve catalyst can be regenerated by simple high-temperature roasting, and the regeneration effect is good.
Detailed Description
The following detailed description of specific embodiments of the present invention is not intended to limit the invention to the particular forms described below:
example 1
Mixing the NaY molecular sieve with 0.3mol/L ammonium chloride solution according to the liquid/solid weight ratio of 3, exchanging for 4 hours at 90 ℃, filtering and leaching the molecular sieve, drying for 5 hours at 105 ℃, and roasting for 5 hours at 500 ℃, and repeating the steps for 3 times to obtain the modified molecular sieve catalyst.
The modified molecular sieve catalyst is filled into a tubular fixed bed, the length-diameter ratio of a catalyst bed layer is 100, and the volume space velocity of circulating methanol (containing 2500ppm of aldehyde and ketone impurities) from the HPPO process is 0.5h-1Pumping into a tubular fixed bed, treating at 75 deg.C and 4MPa, and discharging aldehyde ketone impurity content of 3ppm and acetal ketal content of 4892 ppm. The discharging index of aldehyde and ketone impurities is required to be less than or equal to 8ppm, and the device is operated for 1200 h.
Purging the catalyst to be treated by nitrogen at 400 ℃ under 300 ℃ and 400 ℃ until the content of combustible gas is less than or equal to 10 percent LEL (lower explosion limit in air), then gradually increasing the oxygen content in regenerated gas to 21 percent (namely air atmosphere), continuing to calcine for 8 hours at 450 ℃, evaluating the effect of the modified molecular sieve catalyst again, wherein the content of aldehyde and ketone impurities in the initial discharge is 3ppm, and the operation time of the device is 1300 hours.
Example 2
Mixing the NaY molecular sieve with 0.2mol/L stannous chloride solution according to the liquid/solid weight ratio of 2, exchanging for 8 hours at the temperature of 60 ℃, filtering and leaching the molecular sieve, drying for 5 hours at the temperature of 105 ℃, and roasting for 5 hours at the temperature of 500 ℃, and repeating the steps for 5 times to obtain the modified molecular sieve catalyst.
The modified molecular sieve catalyst is filled into a tubular fixed bed, the length-diameter ratio of a catalyst bed layer is 50, and the circulating methanol (the content of aldehyde and ketone impurities is 1000ppm) from the HPPO process is used at the volume space velocity of 2h-1Pumping into a reactor, processing at 60 ℃ and 3MPa, and initially discharging aldehyde ketone impurity content of 8ppm and acetal ketal content of 1902 ppm. The discharging index of aldehyde and ketone impurities is required to be less than or equal to 12ppm, and the device operation time is 1600 h.
Purging the catalyst to be treated by nitrogen at 400 ℃ under 300 ℃ and 400 ℃ until the content of combustible gas is less than or equal to 10 percent LEL (lower explosion limit in air), then gradually increasing the oxygen content in regenerated gas to 21 percent (namely air atmosphere), continuing to calcine for 6 hours at 500 ℃, evaluating the effect of the modified molecular sieve catalyst again, wherein the content of aldehyde and ketone impurities in the initial discharge is 7ppm, and the operation time of the device is 1500 hours.
Example 3
Mixing an MCM-22 molecular sieve with 0.1mol/L ammonium chloride solution according to the liquid/solid weight ratio of 4, exchanging for 4 hours at the temperature of 95 ℃, filtering and leaching the molecular sieve, drying for 5 hours at the temperature of 105 ℃, and roasting for 7 hours at the temperature of 550 ℃, and repeating the steps for 4 times to obtain the modified molecular sieve catalyst.
The modified molecular sieve catalyst is filled into a tubular fixed bed, the length-diameter ratio of the catalyst bed is 50, and the volume space velocity of the circulating methanol (the content of aldehyde and ketone impurities is 200ppm) from the HPPO process is 4h-1Pumping into a tubular fixed bed, processing at 40 ℃ and 1MPa, and initially discharging aldehyde ketone impurity content of 15ppm and acetal ketal content of 362 ppm. The discharging index of aldehyde and ketone impurities is required to be less than or equal to 20ppm, the running time of the device is 900 h.
Purging the catalyst to be treated by nitrogen at the temperature of 300-400 ℃ until the content of combustible gas is less than or equal to 10 percent LEL (lower explosion limit in air), then gradually increasing the oxygen content in regenerated gas to 21 percent (namely air atmosphere), continuously roasting at the temperature of 550 ℃ for 5 hours, evaluating the effect of the modified molecular sieve catalyst again, wherein the content of aldehyde and ketone impurities in the initial discharge is 13ppm, and the operation time of the device is 1000 hours.
Example 4
Mixing a ZSM-5 molecular sieve with 0.2mol/L ammonium nitrate solution according to the liquid/solid weight ratio of 3, exchanging for 10h at 30 ℃, filtering and leaching the molecular sieve, drying for 5h at 105 ℃, and roasting for 8h at 500 ℃, and repeating the steps for 3 times to obtain the modified molecular sieve catalyst.
The modified molecular sieve catalyst is filled into a tubular fixed bed, the length-diameter ratio of a catalyst bed layer is 40, and the circulating methanol (the content of aldehyde and ketone impurities is 150ppm) from the HPPO process is used at a volume space velocity of 5h-1Pumping into a tubular fixed bed, processing at 50 ℃ and 2MPa, and initially discharging aldehyde ketone impurity content of 12ppm and acetal ketal content of 298 ppm. The discharging index of aldehyde and ketone impurities is required to be less than or equal to 15ppm, and the device operation time is 800 h.
Purging the catalyst to be treated by nitrogen at 400 ℃ under 300 ℃ and 400 ℃ until the content of combustible gas is less than or equal to 10 percent LEL (lower explosion limit in air), then gradually increasing the oxygen content in regenerated gas to 21 percent (namely air atmosphere), continuing to calcine at 550 ℃ for 3 hours, evaluating the effect of the modified molecular sieve catalyst again, wherein the content of aldehyde and ketone impurities in the initial discharge is 13ppm, and the operation time of the device is 900 hours.
Example 5
Mixing the 4A molecular sieve with 0.1mol/L nickel chloride solution according to the liquid/solid weight ratio of 2, exchanging for 3h at 80 ℃, filtering and leaching the molecular sieve, drying for 5h at 105 ℃, and roasting for 3h at 600 ℃, and repeating the steps for 5 times to obtain the modified molecular sieve catalyst.
The modified molecular sieve catalyst is filled into a tubular fixed bed, the length-diameter ratio of the catalyst bed is 60, and the volume space velocity of circulating methanol (the content of aldehyde and ketone impurities is 100ppm) from the HPPO process is 6h-1Pumping into a tubular fixed bed, treating at 50 deg.C and 2MPa, and initiatingThe discharged aldehyde ketone impurity content is 18ppm, and the acetal ketal content is 170 ppm. The discharging index of aldehyde and ketone impurities is required to be less than or equal to 25ppm, and the device is operated for 1000 hours.
Purging the catalyst to be treated by nitrogen at the temperature of 300-400 ℃ until the content of combustible gas is less than or equal to 10 percent LEL (lower explosion limit in air), then gradually increasing the oxygen content in regenerated gas to 21 percent (namely air atmosphere), continuing to calcine at the temperature of 550 ℃ for 4 hours, evaluating the effect of the modified molecular sieve catalyst again, wherein the content of aldehyde and ketone impurities in the initial discharge is 16ppm, and the operation time of the device is 1050 hours.
Example 6
Mixing a Beta molecular sieve with 0.1mol/L zinc chloride solution according to the liquid/solid weight ratio of 2, exchanging for 2h at 90 ℃, filtering and leaching the molecular sieve, drying for 5h at 105 ℃, and roasting for 10h at 400 ℃, and repeating the steps for 5 times to obtain the modified molecular sieve catalyst.
The modified molecular sieve catalyst is filled into a tubular fixed bed, the length-diameter ratio of a catalyst bed layer is 100, and the circulating methanol (the content of aldehyde and ketone impurities is 500ppm) from the HPPO process is used at the volume space velocity of 1h-1Pumping into a tubular fixed bed, processing at 50 ℃ and 2MPa, and initially discharging 58ppm of aldehyde ketone impurities and 882ppm of acetal ketal. The discharging index of aldehyde and ketone impurities is required to be less than or equal to 80ppm, and the device operation time is 1350 h.
Purging the catalyst to be treated by nitrogen at 400 ℃ under 300 ℃ and 400 ℃ until the content of combustible gas is less than or equal to 10 percent LEL (lower explosion limit in air), then gradually increasing the oxygen content in regenerated gas to 21 percent (namely air atmosphere), continuously roasting at 450 ℃ for 4, evaluating the effect of the modified molecular sieve catalyst again, wherein the content of aldehyde and ketone impurities in the initial discharge is 65ppm, and the operation time of the device is 1000 hours.
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (3)
1. A method for removing aldehyde and ketone in circulating methanol of an HPPO process by using a molecular sieve catalytic reaction comprises the following steps:
(1) preparing a modified molecular sieve: the molecular sieve is one or more of ZSM-5, A, MCM and Beta molecular sieves, the modification mode is an ion exchange method, and the modification reagent is Sn2+、Zn2+、Ni2+、NH4 +、Ti4+、Ag+、Co2+One or more of a hydrochloride or nitrate; in the step (1), the liquid/solid weight ratio of ion exchange is 1-5, the temperature is 20-100 ℃, the time is 0.1-10 h/time, the roasting temperature is 300-;
(2) pumping circulating methanol containing aldehyde ketone impurities from an HPPO process into a fixed bed reaction device filled with a modified molecular sieve at a certain airspeed, catalyzing aldehyde ketone and methanol to react by using the modified molecular sieve at a certain temperature and under a certain pressure to generate corresponding acetal and ketal, and obtaining purified circulating methanol without the aldehyde ketone impurities, wherein the circulating methanol contains the aldehyde ketone impurities which are one or a mixture of formaldehyde, acetaldehyde, propionaldehyde and acetone, and the total aldehyde ketone content is 50-5000 ppm; in the step (2), the temperature of the reaction of the circulating methanol in a fixed bed reaction device is 40-80 ℃, and the pressure is 0.5-5 Mpa;
(3) and (4) operating the fixed bed device until the content of the aldehyde and ketone impurities is increased to a certain index, and roasting and regenerating the modified molecular sieve in the regeneration gas.
2. The method for removing aldehyde ketone in circulating methanol in HPPO process by using molecular sieve catalytic reaction according to claim 1, wherein in the step (2), the fixed bed reaction device is a traditional tubular fixed bed, the length-diameter ratio of a single tubular fixed bed is 10-100, the circulating methanol is pumped in a mode of up-in-down-out or down-in-up-out, and the volume space velocity is 0.1-10h-1。
3. The method for removing aldehyde ketone in circulating methanol by using molecular sieve catalytic reaction for HPPO process according to claim 1, wherein in the step (3), the regeneration process comprises purging the catalyst to be treated with nitrogen at 400 ℃ under 300-.
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