CN114618390B - Fixed bed reactor for producing N-methylmorpholine by continuous method - Google Patents
Fixed bed reactor for producing N-methylmorpholine by continuous method Download PDFInfo
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- CN114618390B CN114618390B CN202011445396.2A CN202011445396A CN114618390B CN 114618390 B CN114618390 B CN 114618390B CN 202011445396 A CN202011445396 A CN 202011445396A CN 114618390 B CN114618390 B CN 114618390B
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- China
- Prior art keywords
- fixed bed
- methylmorpholine
- bed reactor
- monomethylamine
- diethylene glycol
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- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000011437 continuous method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000012043 crude product Substances 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 100
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 80
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 238000010924 continuous production Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002085 irritant Substances 0.000 abstract description 2
- 231100000021 irritant Toxicity 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 30
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000005086 pumping Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000012840 feeding operation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a fixed bed reactor for producing N-methylmorpholine by a continuous method, which comprises the following operation steps: s1: copper nitrate trihydrate is dissolved in water, carrier silicon dioxide and water are stirred into slurry in a kettle, sodium carbonate aqueous solution (20%) and copper nitrate solution are added dropwise at the same time, and finally, the slurry solution is ensured to be neutral (PH=7). Compared with a kettle type reactor adopted in the prior art, the fixed bed reactor for producing N-methylmorpholine by a continuous method has the advantages of high reaction selectivity, remarkably improved device production capacity, stable process, more stable product quality, low raw material cost, direct use of the obtained crude product in a rectification step, and acquisition of the product, no generation of corrosive or irritant substances in the production process, and only small amount of water, so that production equipment cannot be corroded, and the fixed bed reactor belongs to clean production and brings better application prospect.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a fixed bed reactor for producing N-methylmorpholine by a continuous method.
Background
N-methylmorpholine is an important organic chemical intermediate, is a colorless to yellow liquid compound with amine taste, has a chemical formula of C5H11NO, has a CAS number of 109-02-4 and a molecular weight of 101.15, has the dual properties of tertiary amine and ether, is widely used as a chemical intermediate, an extractant, a corrosion inhibitor, a surfactant and the like, is widely used as a catalyst for polyester polyurethane soft foam in the polyurethane industry, is used as a solvent (good solvent for dye, cassoe, wax, shellac and the like), is also used as a stabilizer and an analysis reagent for chlorocarbon, is also used for the synthesis of rubber accelerators and other fine chemicals, is used as a spinning solvent for Lyocell (commonly known as tencel) and Newcell rayon filaments which are currently known as green fibers, and is also used as a solvent for producing plant intestines, and has higher and higher requirements on the manufacturing process of N-methylmorpholine along with the continuous development of technology.
The existing N-methylmorpholine has certain disadvantages when in use, firstly, the N-methylmorpholine is synthesized by a plurality of processes, namely a morpholine method, an N-methyldiethanol method, a diethanolamine method, a diglycol method and a dichloroethyl ether method according to raw materials, wherein methylation research is the most on the basis of morpholine as a raw material, the morpholine methylation method is also an important method for synthesizing the N-methylmorpholine, the morpholine as a raw material is high in price, a noble metal catalyst is needed to be used for generating high cost, and a large amount of formaldehyde-containing industrial wastewater is generated, the treatment is difficult, other methods basically adopt concentrated sulfuric acid for dehydration, the three wastes are high, the yield is low, certain adverse effects are brought to the use process of people, the inside of the device cannot be cleaned conveniently, the scaling condition is easy to occur due to overlong use time, and the reaction effect is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a fixed bed reactor for producing N-methylmorpholine by a continuous method, which can realize continuous feeding, and compared with a kettle type reactor adopted in the prior art, the device has obviously improved production capacity and high product content (more than 99.5 percent); in addition, the process route of raw materials diethylene glycol and monomethylamine is adopted, the raw material cost is low, the selectivity of N-methylmorpholine is more than 92%, the bottom can be disassembled and assembled through the lifting mechanism, the interior is convenient to clean, the reaction effect is improved, the sealing performance is excellent, and the problems in the background technology can be effectively solved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the utility model provides a fixed bed reactor for producing N-methylmorpholine by continuous process, includes the fixed bed reactor main part, the upper end fixedly connected with upper cover of fixed bed reactor main part, the upper end fixedly connected with rings and the pan feeding mouth of upper cover, the inside of pan feeding mouth is provided with the entry distributor, the outside fixedly connected with machine oil feed inlet of upper cover, one side fixedly connected with diethylene glycol feed pump and monomethylamine feed pump of fixed bed reactor main part, the opposite side fixedly connected with upper channel mouth and lower floor's channel mouth of fixed bed reactor main part, the inside of fixed bed reactor main part is provided with the retort, the lower extreme outer wall fixedly connected with of fixed bed reactor main part is supporting base No. one and No. two supporting bases, the lower extreme of fixed bed reactor main part is provided with removable bottom, the lower extreme fixedly connected with locating support and the discharge gate of removable bottom, the inside of discharge gate is provided with the exit collector, locating support lower extreme fixedly connected with elevating support.
As a preferable technical scheme, the inside fixedly connected with location chassis of removable bottom, the upper end fixedly connected with location outer lane of removable bottom and location inner circle, the location outer lane is located the outer lane of location inner circle, the outer wall fixedly connected with sealed pad of location inner circle, the upper end swing joint of location chassis has the puddler, the outer wall fixedly connected with stirring vane of puddler.
As a preferable technical scheme, the inner wall of the upper end of the fixed bed reactor main body is fixedly connected with a multifunctional distribution plate, the inside of the multifunctional distribution plate is fixedly connected with a distribution frame, the outer wall of the multifunctional distribution plate is fixedly connected with a fixing frame, the lower end of the multifunctional distribution plate is provided with a depositor, threads and a clamping ring are arranged between the multifunctional distribution plate and the depositor, and the outer wall of the depositor is provided with a filtrate port.
As a preferable technical scheme, a first fixing frame is arranged between the fixed bed reactor main body and the diethylene glycol feed pump and the monomethylamine feed pump, one side of the fixed bed reactor main body is fixedly connected with one ends of the diethylene glycol feed pump and the monomethylamine feed pump through the first fixing frame, a second fixing frame is arranged between the fixed bed reactor main body and the upper layer passage opening and between the fixed bed reactor main body and the lower layer passage opening, and the other side of the fixed bed reactor main body is fixedly connected with one end of the lower layer passage opening through the second fixing frame.
As a preferable technical scheme, a positioning seat is arranged between the detachable bottom cover and the positioning inner ring and the positioning outer ring, the upper end of the detachable bottom cover is fixedly connected with the lower ends of the positioning inner ring and the positioning outer ring through the positioning seat, a strong adhesive is arranged between the positioning inner ring and the sealing gasket, and the outer surface of the positioning inner ring is fixedly connected with the inner surface of the sealing gasket through the strong adhesive.
As a preferable technical scheme, the lower end of the multifunctional distribution plate is detachably connected with the upper end of the depositor through threads and a clamping ring, a positioning piece is arranged between the multifunctional distribution plate and the distribution frame, and the inside of the multifunctional distribution plate is fixedly connected with the outer wall of the distribution frame through the positioning piece.
As a preferable embodiment, the fixed bed reactor body is formed by stacking silica supported copper catalyst particles having a particle diameter of Φ5× (4 to 5) mm, the silica supported copper catalyst comprising the following components in parts by weight: 20-60% of copper and 30-80% of silicon dioxide.
As a preferable technical scheme, the internal reaction temperature of the fixed bed reactor main body is 200-260 ℃, the internal reaction pressure of the fixed bed reactor main body is 0.5-1.0Mpa, and the circulation gas quantity of a circulating pump in the fixed bed reactor main body is 30-60L/h.
Compared with the prior art, the invention provides a fixed bed reactor for producing N-methylmorpholine by a continuous method, which has the following beneficial effects: the fixed bed reactor for producing the N-methylmorpholine by the continuous method has the advantages that the bottom can be disassembled and assembled through the lifting mechanism, the inside can be conveniently cleaned, the reaction effect is improved, the sealing performance is excellent, continuous feeding can be realized, compared with a kettle type reactor adopted in the prior art, the reaction selectivity is high, the device production capacity is remarkably improved, the process is stable, the product quality is more stable, in addition, the raw material cost is low, the obtained crude product is directly used for a rectification step, the product is obtained, excessive monomethylamine can be recycled, the operation is simple, no corrosive or irritant substance is generated in the production process, only a small amount of water is generated, therefore, the corrosion to production equipment and environmental pollution are avoided, the continuous feeding can be realized, the device production capacity is remarkably improved, and the product content is high (more than 99.5 percent) compared with the kettle type reactor adopted in the prior art; in addition, the process route of raw materials diethylene glycol and monomethylamine is adopted, the raw material cost is low, the selectivity of N-methylmorpholine is more than 92%, the fixed bed reactor provided by the invention can continuously produce N-methylmorpholine, the purity of crude products reaches more than 95.9%, the yield is more than 95%, the crude products are semi-finished products, the conversion rate of target products represented by the crude products is high, the conversion rate is high, the yield is high, the whole N-methylmorpholine has a simple structure, the operation is convenient, and the use effect is better than that of the traditional method.
Drawings
FIG. 1 is a schematic diagram showing the overall structure of a fixed bed reactor for producing N-methylmorpholine by a continuous process according to the present invention.
FIG. 2 is a schematic diagram of a removable base of a fixed bed reactor for continuous production of N-methylmorpholine according to the invention.
FIG. 3 is a schematic diagram of a multifunctional distributor plate of a fixed bed reactor for continuous production of N-methylmorpholine according to the invention.
FIG. 4 is a schematic diagram of a depositor of a fixed bed reactor for continuous production of N-methylmorpholine according to the invention.
FIG. 5 is a schematic diagram showing the overall structure of a fixed bed reactor for producing N-methylmorpholine by a continuous process according to the present invention.
FIG. 6 is a schematic structural diagram of the target product N-methylmorpholine in a fixed bed reactor for continuous production of N-methylmorpholine according to the invention.
FIG. 7 is a schematic diagram of the structure of a study of copper loading in a fixed bed reactor for continuous production of N-methylmorpholine according to the invention.
FIG. 8 is a schematic structural diagram of an analysis table of examination results in a fixed bed reactor for producing N-methylmorpholine by a continuous process according to the present invention.
FIG. 9 is a schematic structural diagram of a crude product investigation result analysis table in a fixed bed reactor for producing N-methylmorpholine by a continuous process according to the invention.
In the figure: 1. a fixed bed reactor body; 2. a hanging ring; 3. a liquid inlet; 4. diethylene glycol feed pump; 5. a methylamine feed pump; 6. a first support base; 7. an outlet collector; 8. a discharge port; 9. a feed inlet; 10. an inlet distributor; 11. an upper cover; 12. a dispensing rack; 13. an upper layer passage port; 14. a reaction tank; 15. a lower layer passage port; 16. a detachable bottom cover; 17. a second support base; 18. lifting the support; 19. stirring sheets; 20. positioning an inner ring; 21. positioning an outer ring; 22. a positioning bracket; 23. a stirring rod; 24. a sealing gasket; 25. positioning a chassis; 26. a fixing frame; 27. a multi-functional distribution tray; 28. a depositor; 29. a filtrate port; 30. a thread; 31. and a collar.
Description of the embodiments
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
As shown in fig. 1-9, a fixed bed reactor for producing N-methylmorpholine by a continuous process comprises a fixed bed reactor main body 1, wherein an upper cover 11 is fixedly connected to the upper end of the fixed bed reactor main body 1, a lifting ring 2 and a feed inlet 9 are fixedly connected to the upper end of the upper cover 11, an inlet distributor 10 is arranged in the feed inlet 9, an engine oil feed inlet 3 is fixedly connected to the outer side of the upper cover 11, a diethylene glycol feed pump 4 and a monomethylamine feed pump 5 are fixedly connected to one side of the fixed bed reactor main body 1, an upper layer channel port 13 and a lower layer channel port 15 are fixedly connected to the other side of the fixed bed reactor main body 1, a reaction tank 14 is arranged in the fixed bed reactor main body 1, a first supporting base 6 and a second supporting base 17 are fixedly connected to the outer wall of the lower end of the fixed bed reactor main body 1, a detachable bottom cover 16 is arranged at the lower end of the fixed bed reactor main body 1, a positioning bracket 22 and a discharge outlet 8 are fixedly connected to the lower end of the detachable bottom cover 16, an outlet collector 7 is arranged in the inner side of the discharge outlet 8, and a lifting support 18 is fixedly connected to the lower end of the positioning bracket 22.
Further, the inside fixedly connected with location chassis 25 of removable bottom 16, the upper end fixedly connected with location outer lane 21 and the location inner circle 20 of removable bottom 16, location outer lane 21 are located the outer lane of location inner circle 20, the outer wall fixedly connected with sealed pad 24 of location inner circle 20, the upper end swing joint of location chassis 25 has puddler 23, the outer wall fixedly connected with stirring piece 19 of puddler 23 is convenient for carry out dismouting cleaning operation.
Further, the inner wall of the upper end of the fixed bed reactor main body 1 is fixedly connected with a multifunctional distribution plate 27, the inside of the multifunctional distribution plate 27 is fixedly connected with a distribution frame 12, the outer wall of the multifunctional distribution plate 27 is fixedly connected with a fixing frame 26, the lower end of the multifunctional distribution plate 27 is provided with a sediment device 28, threads 30 and a clamping ring 31 are arranged between the multifunctional distribution plate 27 and the sediment device 28, the outer wall of the sediment device 28 is provided with a filtrate port 29, and materials are filtered conveniently and better.
Further, a first fixing frame is arranged between the fixed bed reactor main body 1 and the diethylene glycol feed pump 4 and the monomethylamine feed pump 5, one side of the fixed bed reactor main body 1 is fixedly connected with one ends of the diethylene glycol feed pump 4 and the monomethylamine feed pump 5 through the first fixing frame, a second fixing frame is arranged between the fixed bed reactor main body 1 and the upper layer channel opening 13 and between the fixed bed reactor main body 1 and the lower layer channel opening 15, and the other side of the fixed bed reactor main body 1 is fixedly connected with one end of the lower layer channel opening 15 through the second fixing frame, so that material feeding operation is facilitated.
Further, a positioning seat is arranged between the detachable bottom cover 16 and the positioning inner ring 20 and the positioning outer ring 21, the upper end of the detachable bottom cover 16 is fixedly connected with the lower ends of the positioning inner ring 20 and the positioning outer ring 21 through the positioning seat, a strong adhesive is arranged between the positioning inner ring 20 and the sealing gasket 24, and the outer surface of the positioning inner ring 20 is fixedly connected with the inner surface of the sealing gasket 24 through the strong adhesive, so that the sealing disassembly is convenient.
Further, the lower end of the multifunctional distribution plate 27 is detachably connected with the upper end of the depositor 28 through threads 30 and a clamping ring 31, a positioning piece is arranged between the multifunctional distribution plate 27 and the distribution frame 12, and the inside of the multifunctional distribution plate 27 is fixedly connected with the outer wall of the distribution frame 12 through the positioning piece, so that distribution operation is facilitated.
Further, the fixed bed reactor main body 1 is formed by stacking silica supported copper catalyst particles with a particle diameter of Φ5×4 to 5mm, and the silica supported copper catalyst is composed of the following components in parts by weight: 20-60% of copper and 30-80% of silicon dioxide.
Further, the reaction temperature in the fixed bed reactor main body 1 is 200-260 ℃, the reaction pressure in the fixed bed reactor main body 1 is 0.5-1.0Mpa, and the circulation gas amount of a circulating pump in the fixed bed reactor main body 1 is 30-60L/h.
Examples
The fixed bed reactor main body 1 is formed by stacking silicon dioxide supported copper catalyst particles with the particle size of phi 5X (4-5) mm, and the thickness is 40cm; silica supported copper catalyst composition (weight): copper 35% and silica 65%.
Examples
The fixed bed reactor main body 1 is formed by stacking silicon dioxide supported copper catalyst particles with the particle size of phi 5X (4-5) mm, and the thickness is 60cm; silica supported copper catalyst composition (weight): 45% of copper and 55% of silicon dioxide.
Example 3: reduction and pretreatment of the catalyst: after the fixed bed reactor main body 1 is filled, the pressure is tested at 1.8-2.0MPa, no obvious air leakage exists, nitrogen and hydrogen are replaced, mixed gas with the volume ratio of nitrogen to hydrogen of 4:1 passes through a catalyst bed layer, the catalyst bed layer is gradually heated to 280 ℃ and continuously aged for 72 hours, and then the temperature is reduced to 220 ℃ for standby, so that N-methylmorpholine is prepared: filling hydrogen into a fixed bed reactor to 0.4Mpa, stabilizing the temperature of a bed layer at about 220 ℃, continuously pumping monomethylamine (the pumping speed is 4 ml/min) through a metering pump, starting a circulating pump, circulating reaction gas, adjusting a frequency converter to ensure that the circulating gas quantity is 30L/h, sampling and detecting that the monomethylamine concentration is more than 40% after 2 hours, continuously pumping raw material diethylene glycol into a tubular reactor of the fixed bed reactor with a copper-filled catalyst bed layer through the metering pump, carrying out gas-liquid-solid three-phase reaction, simultaneously reducing the flow rate of monomethylamine to 0.6ml/min, reducing the flow rate of diethylene glycol to 1ml/min, and carrying out the molar ratio monomethylamine: diethylene glycol=1.24:1, the reaction temperature is 220 ℃, the reaction pressure is 0.8-0.9 MPa, a high-pressure circulating gas pump circulates the reaction gas at 30L/h, after continuous reaction for 6 hours, the materials are cooled by a condenser, a liquid-phase crude product is discharged, the crude product is heated to remove redundant monomethylamine (monomethylamine is recycled), a small amount of generated water is separated to obtain 400g of liquid, the liquid is analyzed by GC, diethylene glycol is 2.3%, methylmorpholine is 94.2%, and morpholine is 2.2%. The crude product is rectified by a 80cm rectification column to obtain 358g of finished product (content: 99.5%) with a yield of 93.5%.
Example 4: reduction and pretreatment of the catalyst: after the fixed bed catalyst (prepared according to the method of example 1) is filled, the pressure is tested at 1.8-2.0MPa, no obvious leakage exists, and after the nitrogen and hydrogen are replaced, nitrogen is used: the mixed gas of hydrogen=4:1 (volume ratio) passes through a catalyst bed, the catalyst bed is gradually heated to 280 ℃ and continuously aged for 72 hours, then cooled to 240 ℃ for standby, and the N-methylmorpholine is prepared: filling hydrogen into a fixed bed reactor to 0.4Mpa, stabilizing the temperature of a bed layer at about 220 ℃, continuously pumping monomethylamine (the pumping speed is 4 ml/min) through a metering pump, starting a circulating pump, circulating reaction gas, adjusting a frequency converter to ensure that the circulating gas quantity is 50L/h, sampling and detecting that the monomethylamine concentration is more than 40% after 2 hours, continuously pumping raw material diethylene glycol into a tubular reactor of the fixed bed reactor with a copper-filled catalyst bed layer through the metering pump, carrying out gas-liquid-solid three-phase reaction, simultaneously reducing the flow rate of monomethylamine to 1ml/min, reducing the flow rate of diethylene glycol to 1ml/min, and carrying out the molar ratio monomethylamine: diethylene glycol=2:1, the reaction temperature is 240 ℃, the reaction pressure is 0.5-0.6 MPa, a high-pressure circulating gas pump circulates the reaction gas at 50L/h, after continuous reaction for 6 hours, the materials are cooled by a condenser, a liquid-phase crude product is discharged, the crude product is heated to remove redundant monomethylamine (monomethylamine is recycled), a small amount of generated water is separated to obtain liquid 398g, the liquid is analyzed by GC, diethylene glycol is 1.4%, methylmorpholine is 95.4% and morpholine is 2.2%. The crude product is rectified by a 80cm rectifying column to obtain 360g of finished product (content: 99.6%), and the yield is 94%.
Example 5: reduction and pretreatment of the catalyst: after the fixed bed reactor main body 1 is filled, the pressure is tested under 1.8-2.0MPa, no obvious air leakage exists, and after the replacement of nitrogen and hydrogen, nitrogen is used: the mixed gas of hydrogen=4:1 (volume ratio) passes through a catalyst bed, the catalyst bed is gradually heated to 280 ℃ and continuously aged for 72 hours, then cooled to 260 ℃ for standby, and the N-methylmorpholine is prepared: filling hydrogen into a fixed bed reactor to 0.4Mpa, stabilizing the temperature of a bed layer at about 240 ℃, continuously pumping monomethylamine (the pumping speed is 4 ml/min) through a metering pump, starting a circulating pump, circulating reaction gas, adjusting a frequency converter to ensure that the circulating gas quantity is 60L/h, sampling and detecting that the monomethylamine concentration is more than 40% after 2 hours, continuously pumping raw material diethylene glycol into a tubular reactor of the fixed bed reactor with a copper-filled catalyst bed layer through the metering pump, carrying out gas-liquid-solid three-phase reaction, simultaneously reducing the flow rate of monomethylamine to 3ml/min, reducing the flow rate of diethylene glycol to 1ml/min, and carrying out the molar ratio monomethylamine: diethylene glycol=6.1:1, the reaction temperature is 260 ℃, the reaction pressure is 0.7-0.8 MPa, a high-pressure circulating gas pump circulates the reaction gas at 60L/h, after continuous reaction for 6 hours, the materials are cooled by a condenser, a liquid-phase crude product is discharged, the crude product is heated to remove redundant monomethylamine (monomethylamine is recycled), a small amount of generated water is separated, so as to obtain liquid 401g, GC analysis, diethylene glycol 0.4%, methylmorpholine 95.9% and morpholine 1.2%. The crude product is rectified by a 80cm rectifying column to obtain 365g of finished product (content: 99.6%), the yield is 95.3%, the fixed bed reactor provided by the invention can continuously produce N-methylmorpholine, the purity of the crude product is more than 95.9%, the yield is more than 95%, the crude product is a semi-finished product, and the conversion rate, the conversion rate and the yield of the target product represented by the crude product are high.
Working principle: the invention comprises a fixed bed reactor main body 1, a lifting ring 2, a liquid inlet 3, a diethylene glycol feed pump 4, a monomethylamine feed pump 5, a first supporting base 6, an outlet collector 7, a discharge outlet 8, a feed inlet 9, an inlet distributor 10, an upper cover 11, a distribution frame 12, an upper layer passage opening 13, a reaction tank 14, a lower layer passage opening 15, a detachable bottom cover 16, a second supporting base 17, a lifting support 18, a stirring sheet 19, a positioning inner ring 20, a positioning outer ring 21, a positioning support 22, a stirring rod 23, a sealing gasket 24, a positioning chassis 25, a fixing frame 26, a multifunctional distribution disc 27, a depositor 28, a filtrate opening 29, threads 30 and a clamping ring 31, when in use, diethylene glycol and monomethylamine are input into the fixed bed reactor main body 1 through the diethylene glycol feed pump 4 and the monomethylamine feed pump 5, reaction is carried out in the reaction tank 14, and the materials enter from the position of the feed inlet 9, the discharge operation is carried out from the position of the discharge hole 8 after the reaction is carried out through the distribution of the inlet distributor 10, the outlet collector 7 has the effect of the discharge distribution, the first support base 6 and the second support base 17 are convenient for carrying out the support operation, when the cleaning is carried out, the position of the lifting support 18 is lowered to drive the detachable bottom cover 16, the positioning inner ring 20 and the positioning outer ring 21 to descend so as to separate from the fixed bed reactor main body 1, the positioning inner ring 20 and the positioning outer ring 21 respectively clamp the position of the fixed bed reactor main body 1, the sealing gasket 24 has good sealing effect and prevents the leakage, the stirring rod 23 rotates at the upper end of the positioning chassis 25, the stirring sheet 19 is used for stirring, the material liquid enters from the position of the feed inlet 9 and then enters the position of the multifunctional distribution disc 27 for carrying out the material distribution operation, the deposition is carried out through the deposition device 28, the filtrate port 29 is convenient for discharging the feed liquid, filtering impurities, is more practical, dissolving Cu (NO 3) 2.3H2O in water, stirring carrier silicon dioxide and water into slurry in a kettle, simultaneously dropwise adding sodium carbonate aqueous solution (20%) and copper nitrate solution, finally ensuring that the slurry solution is neutral (PH=7), ageing in a water bath at 50+/-5 ℃ for 5+/-1H, centrifuging, adding the extrusion aid sesbania powder into a filter cake, uniformly stirring a small amount of water, extruding and forming by a strip extruder, cutting into cylinders with the size of 5mm, drying, roasting for 10H at 500 ℃, cooling to normal temperature for standby, taking diethylene glycol and monomethylamine as raw materials, continuously pumping diethylene glycol and monomethylamine into a feed through a diethylene glycol feed pump 4 and a monomethylamine feed pump 5, wherein the molar ratio of diethylene glycol to monomethylamine is 1:1.2-8, the pumping speed of diethylene glycol is 1-3ml/min, the pumping speed of monomethylamine is 0.6-6ml/min, the system reaction pressure is 0.5-1.0MPa, the reaction temperature is 200-260 ℃, the circulation gas amount of a circulating pump is 30-60L/H, and obtaining the N-methylmorpholine crude product after the reaction is finished.
It should be noted that in this document, relational terms such as first and second (first and second), and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. A process for the continuous production of N-methylmorpholine, characterized in that: the method comprises the following operation steps:
s1: dissolving copper nitrate trihydrate in water, stirring carrier silicon dioxide and water into slurry in a kettle, simultaneously dropwise adding sodium carbonate aqueous solution and copper nitrate solution, and finally ensuring that the slurry solution is neutral;
s2: aging in water bath at 50+ -5deg.C for 5+ -1 hr, centrifuging, adding sesbania powder as adjuvant into the filter cake, stirring with small amount of water, extruding with strip extruder, cutting into cylinders of 5mm x 5mm, oven drying, calcining at 500deg.C for 10 hr, and cooling to room temperature;
s3: diethylene glycol and monomethylamine are used as raw materials, diethylene glycol and monomethylamine are continuously pumped into a feeding material through a metering pump, and the molar ratio of diethylene glycol to monomethylamine is 1:2-6.1;
s4: diethylene glycol is pumped at a speed of 1-3ml/min, monomethylamine is pumped at a speed of 0.6-6ml/min, the reaction pressure of the system is 0.5-1.0MPa, the reaction temperature is 240-260 ℃, and the circulation gas amount of a circulating pump is 30-60L/h;
s5: obtaining a crude product of N-methylmorpholine after the reaction is finished, and condensing the material after the fixed bed reaction to obtain the crude product of N-methylmorpholine;
the fixed bed reactor is formed by stacking silicon dioxide supported copper catalyst particles with the particle size of phi 5X (4-5) mm, wherein the silicon dioxide supported copper catalyst comprises the following components in parts by weight: 30-40 wt% of copper and 60-70% of silicon dioxide.
2. A process for the continuous production of N-methylmorpholine according to claim 1 characterized in that: the selectivity of the N-methylmorpholine is more than 92%.
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