CN112225631B - Novel catalytic process for alkylation of arylamine aromatic hydrocarbon - Google Patents
Novel catalytic process for alkylation of arylamine aromatic hydrocarbon Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 21
- 230000029936 alkylation Effects 0.000 title claims abstract description 20
- -1 arylamine aromatic hydrocarbon Chemical class 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 238000012546 transfer Methods 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 32
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 81
- 230000005291 magnetic effect Effects 0.000 claims description 42
- 238000009413 insulation Methods 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- 150000004982 aromatic amines Chemical class 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
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- 238000004821 distillation Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003302 ferromagnetic material Substances 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- 230000002152 alkylating effect Effects 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008602 contraction Effects 0.000 abstract description 9
- 238000001125 extrusion Methods 0.000 abstract description 5
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- 239000003921 oil Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 230000009972 noncorrosive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B01J35/33—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
-
- 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
Abstract
The invention discloses a novel catalytic process for aromatic amine aromatic hydrocarbon alkylation, which belongs to the technical field of chemical synthesis, and can realize the innovative introduction of a novel catalyst, wherein the novel catalyst comprises a molecular sieve catalyst and a heat transfer catalytic fiber rod, the molecular sieve catalyst adopts an acid center formed by protonic acid and non-protonic acid to be attached to the surface of a molecular sieve to form a catalyst with high activity and long service life, the catalyst is applied to a fixed bed reactor, the reaction process and the catalyst are fluorine-free and chlorine-free, and can be recycled without back washing, and the introduced heat transfer catalytic fiber rod can improve the problem of poor heat transfer performance in the fixed bed reactor, so that the rapid conduction and uniform distribution of heat can be realized, and the self expansion and contraction actions can be triggered by heat, thereby the flow of reactant gas in a local range is caused, the catalytic reaction effect is improved by the contact of extrusion gas and the molecular sieve catalyst, and the efficient continuous production of alkylbenzene is realized.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a novel catalytic process for aromatic amine aromatic hydrocarbon alkylation.
Background
The high carbon (C20-24) alkylbenzene is obtained by taking C20-24 alpha olefin as a raw material and carrying out alkylation reaction on the raw material and benzene through a catalyst. Sulfonating high-carbon alkylbenzene with sulfur trioxide to obtain high-carbon alkylbenzene sulfonic acid (HLABS), and neutralizing and carbonating to obtain high-carbon alkylbenzene sulfonic acid calcium (HLABS-Ca).
The calcium higher alkylbenzene sulfonate is one kind of lubricating oil detergent and is mainly used in producing detergent T106. T106 has good high-temperature thermal stability, oil solubility, anti-foaming property and water resistance. High alkali number, strong acid neutralizing power, good detergency and antirust performance. The calcium-based grease is mainly used for preparing marine oil, medium and high grade gasoline internal combustion engine oil and high temperature lubrication calcium-based grease. The base number of T106 is an important index for measuring the product quality, and the T106 on the market at present has two base numbers: TBN300 and TBN400, the higher the base number is, the higher the additional value is, the highest base number of the alkylbenzene byproduct calcium heavy alkylbenzene sulfonate can only reach 360, and TBN400 can only be realized by adding certain high-carbon calcium alkylbenzene sulfonate.
The addition proportion of T106 in the vehicle oil is 3-5%, and the demand will further increase with the increasing environmental protection requirement. The addition ratio of the additive in the marine oil is about 30 percent. The proportion of the high-temperature grease is about 40% or more.
Hydrofluoric acid has been the primary catalyst for linear alkylbenzene production since the 1968 payol unit of UOP was put into operation. Although hydrofluoric acid has significant advantages in efficiency and product quality over the aluminum catalyst, efforts have been made to replace liquid acid with heterogeneous catalysts due to the higher capital and maintenance costs associated with the corrosive nature of the catalyst.
At present, some enterprises adopt solid aluminum trichloride or aluminum trichloride ionic liquid as an alkylation catalyst, and the process has serious environmental protection problems and product quality problems and is difficult to realize large-area industrialization. The new digital process introduced by UOP in 1990 uses a non-corrosive solid catalyst (F-SiO 2-Al2O 3) to effect the alkylation of benzene and normal olefins to produce linear alkylbenzenes. The reactor is a fixed bed reactor, the reactants maintain a liquid phase for operation, and the reaction conditions are mild. The Detal process greatly simplifies the design, operation, safety protection and other problems of the alkylation device, and does not need special metal materials, pumps, valves and the like. The investment in the digital plant can be reduced by 30% compared to the HF alkylation plant. Retrofitting a digital plant to an existing HF alkylation plant, if necessary to retrofit or increase existing processing capacity, is economically attractive. The catalyst used in the digital process has high activity and high selectivity, but in the existing production process, the adopted clay catalyst can carry a large amount of amine substances after being used, so that a large amount of waste residues are generated, the environmental pollution is large, and the operation cost is high.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a novel catalytic process for aromatic amine aromatic alkylation, which can creatively introduce a novel catalyst on the basis of the existing production process, wherein the novel catalyst comprises a molecular sieve catalyst and a heat transfer catalytic fiber rod, the molecular sieve catalyst adopts an acid center formed by protonic acid and non-protonic acid to be attached to the surface of a molecular sieve to form a catalyst with high activity and long service life, the catalyst is applied to a fixed bed reactor, the reaction process and the catalyst are fluorine-free and chlorine-free, and can be repeatedly utilized without back washing, the introduced heat transfer catalytic fiber rod can improve the problem of poor heat transfer performance in the fixed bed reactor, not only can the rapid conduction and the uniform distribution of heat be realized, but also the heat can trigger the self expansion and contraction actions, so that the flow of reactant gas is caused in a local range, and the catalytic reaction effect is improved by extruding the contact of the gas and the molecular sieve catalyst, thereby realizing the efficient continuous production of alkylbenzene.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A novel catalytic process for alkylating aromatic amine aromatic hydrocarbon comprises the following steps:
s1, adding benzene and long-chain olefin into a dehydration tower in proportion, and after reflux dehydration, allowing the mixture to enter a dryer for drying treatment;
s2, heating the dried raw materials to 130-180 ℃ through a reaction heating furnace, and fully reacting in an alkylbenzene reactor under the catalysis of a novel catalyst to obtain a reaction product;
s3, allowing the reaction product to enter a debenzolization tower, distilling at normal pressure to remove unreacted benzene, and recycling;
and S4, removing light components and heavy components in the reaction product by subjecting the reaction product after benzene removal to light component removal and heavy component removal through reduced pressure distillation in a light component removal tower and a heavy component removal tower in sequence to obtain a pure alkylbenzene product.
Further, the molar ratio of benzene to long-chain olefin in the step S1 is 1:2-2.5, and the drying temperature of the dryer is 80-90 ℃.
Further, the alkylbenzene reactor in the step S2 is a fixed bed reactor, the novel catalyst is a mixture of a molecular sieve catalyst and a heat transfer catalytic fiber rod, and the mixing mass ratio is 1.5-0.8.
Further, the molecular sieve catalyst adopts acidic centers formed by protonic acid or aprotic acid to be attached to the surface of a molecular sieve taking zeolite as a raw material, specifically, the protonic acid or the aprotic acid is used for carrying out saturated impregnation on the zeolite at the temperature of 20-80 ℃, then, dehydration drying is carried out at the temperature of 80-250 ℃, then, a nano magnetic iron oxide solution is taken for carrying out saturated impregnation at the temperature of 20-60 ℃, and finally, dehydration drying is carried out at the temperature of 80-120 ℃, so that the zeolite can be modified to endow high activity, high catalytic performance and certain magnetism for being matched with a heat transfer catalytic fiber rod.
Further, the mass ratio of the molecular sieve, the protonic acid or the non-protonic acid and the nano magnetic iron oxide solution is 1.
Further, the molecular sieve catalyst accounts for 5-10% of the mass fraction of the benzene and the long-chain olefin.
Further, the heat transfer catalytic fiber rod comprises a heat insulation fiber sleeve, a pneumatic control ball embedded in the center of the heat insulation fiber sleeve and a pair of heat conduction wires connected to two ends of the inner side of the heat insulation fiber sleeve, the outer end of the pneumatic control ball is connected with a pair of heat insulation columns which are symmetrically distributed, one end of each heat insulation column, far away from the heat insulation ball, is connected with the heat insulation ball, a plurality of heat conduction holes which are uniformly distributed are formed in the heat insulation ball, matched heat conduction magnetic balls are movably embedded in the heat conduction holes, a heat conduction outer bag is arranged in the heat insulation ball, the heat conduction magnetic balls are connected to the outer surface of the heat conduction outer bag, the heat conduction outer bag penetrates through the heat insulation columns and extends into the pneumatic control ball, a heat conduction inner bag corresponding to the heat conduction wires is embedded in the outer end of the pneumatic control ball, the heat conduction inner bag is communicated with the heat conduction outer bag, the heat transfer catalytic fiber rod is filled between molecular sieve catalysts, and absorbs heat through the heat conduction magnetic balls, then the heat is transferred to the air control ball through the heat conduction outer bag, after the air control ball is thermally expanded, on one hand, the heat conduction mixture in the heat conduction outer bag is absorbed through the hydraulic suction force of the heat conduction inner bag, the heat conduction magnetic ball is forced to migrate to the inside from the surface of the heat insulation ball along with the contraction of the heat conduction outer bag, the absorption of external heat is reduced, at the moment, the heat conduction inner bag is contacted with the heat conduction wire under the expansion action of the air control ball after absorbing the heat conduction mixture, so that heat conduction connection is formed, the heat conduction wire transfers the heat on the heat conduction outer bag and the air control ball, so that the heat transfer performance and the heat distribution uniformity inside the reactor are improved, on the other hand, after the air control ball is expanded, the reaction gas in the area can be extruded to the two sides, the reaction gas is just extruded into the inside of the molecular sieve catalyst to be fully contacted with gas and solid, so that the catalytic performance is effectively improved, and the shape of the air control ball is restored after the heat is conducted away by the heat conduction wire, the heat-conducting mixture in the heat-conducting inner bag returns to the heat-conducting outer bag after the heat-conducting inner bag is extruded, the heat-conducting magnetic ball is reset at the same time, a large amount of heat is absorbed again, and the next round of extrusion is started, so that continuous expansion and contraction actions are formed.
Furthermore, the heat conduction oil and the heat conduction sand with the mass ratio of 1:1 are filled in the heat conduction outer bag, the part of the heat conduction outer bag extending into the air control ball and the heat conduction inner bag are both in a compressed state, and the heat conduction oil and the heat conduction sand have good heat conductivity and have certain fluidity to migrate.
Further, heat conduction magnetic ball includes the heat conduction shell and inlays the magnetic core ball in the heat conduction shell, the heat conduction shell adopts the heat conduction material to make, the magnetic core ball adopts ferromagnetic material to make, and the heat conduction shell is used for absorbing the heat and conducts to heat conduction outer bag department, and the magnetic core ball is used for carrying out the cooperation of magnetism with the molecular sieve catalyst, not only is favorable to the resetting of heat conduction magnetic ball, can improve heat-conduction simultaneously.
Furthermore, the heat insulation fiber sleeve, the heat insulation column and the heat insulation ball are all made of heat insulation materials, and the heat conduction magnetic ball is made of thermal expansion materials.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The scheme can realize that a novel catalyst is innovatively introduced on the basis of the existing production process, the novel catalyst comprises a molecular sieve catalyst and a heat transfer catalytic fiber rod, the molecular sieve catalyst adopts an acid center formed by protonic acid and non-protonic acid to be attached to the surface of a molecular sieve, so that the catalyst with high activity and long service life is formed, the catalyst is applied to a fixed bed reactor, the reaction process and the catalyst are fluorine-free and chlorine-free, and can be recycled without backwashing, the introduced heat transfer catalytic fiber rod can improve the problem of poor heat transfer performance in the fixed bed reactor, the rapid heat transfer and uniform heat distribution can be realized, the self expansion and contraction actions can be triggered by heat, the flowing of reactant gas can be caused in a local range, the catalytic reaction effect can be improved by the contact of extrusion gas and the molecular sieve catalyst, and the efficient continuous production of alkylbenzene can be realized.
(2) The heat transfer catalytic fiber rod is filled between molecular sieve catalysts, absorbs heat through the heat conducting magnetic ball, then transfers the heat to the air control ball through the heat conducting outer bag, after the air control ball is thermally expanded, on one hand, the heat conducting mixture in the heat conducting outer bag is absorbed through the hydraulic suction force of the heat conducting inner bag, the heat conducting magnetic ball is forced to migrate from the surface of the heat insulating ball to the inside along with the contraction of the heat conducting outer bag, so that the absorption of external heat is reduced, at the moment, the heat conducting inner bag is contacted with the heat conducting wire under the expansion action of the air control ball after absorbing the heat conducting mixture, so that heat conducting connection is formed, the heat conducting wire transfers the heat on the heat conducting outer bag and the air control ball, so that the heat conductivity and the heat distribution uniformity inside the reactor are improved, on the other hand, after the air control ball is expanded, the reaction gas in the area can be extruded towards two sides, the reaction gas just extrudes into the inside of the molecular sieve catalysts to be fully in gas-solid contact, so that the catalytic performance is effectively improved, after the heat conducting wire conducts the heat away, the heat in the heat conducting inner bag returns to the heat conducting outer bag, the magnetic ball also simultaneously, and the magnetic ball is reset, so that a large amount of heat is continuously extruded, so that the heat conducting ball is continuously extruded, so that the heat is continuously extruded heat is formed.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a schematic diagram of the structure of an alkylbenzene reactor according to this invention;
FIG. 3 is a schematic view of the normal configuration of the heat transfer catalytic fiber rod of the present invention;
FIG. 4 is a schematic diagram of the structure A in FIG. 3;
FIG. 5 is a schematic structural view of the heat transfer catalytic fiber rod of the present invention in an expanded state;
FIG. 6 is a schematic structural view of the pneumatic control ball of the present invention in a normal state;
FIG. 7 is a schematic structural view of the pneumatic control ball of the present invention in an inflated state;
FIG. 8 is a schematic structural view of a thermally conductive magnetic ball according to the present invention.
The reference numbers in the figures illustrate:
1 heat transfer catalytic fiber rod, 11 heat insulation fiber sleeves, 12 heat conduction wires, 13 air control balls, 14 heat insulation columns, 15 heat insulation balls, 2 heat conduction magnetic balls, 21 heat conduction shells, 22 magnetic core balls, 3 heat conduction outer bags and 4 heat conduction inner bags.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is to be understood that the embodiments described are merely exemplary embodiments, rather than exemplary embodiments, and that all other embodiments may be devised by those skilled in the art without departing from the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top/bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "sleeved/connected," "connected," and the like are to be construed broadly, e.g., "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
Example 1:
referring to fig. 1-2, a novel catalytic process for the alkylation of aromatic amines with aromatics comprises the following steps:
s1, adding benzene and long-chain olefin into a dehydration tower in proportion, and after reflux dehydration, allowing the mixture to enter a dryer for drying treatment;
s2, heating the dried raw materials to 130 ℃ through a reaction heating furnace, and fully reacting in an alkylbenzene reactor under the catalysis of a novel catalyst to obtain a reaction product;
s3, allowing the reaction product to enter a debenzolization tower, distilling at normal pressure to remove unreacted benzene, and recycling;
and S4, removing light components and heavy components in the reaction product by subjecting the reaction product after benzene removal to light component removal and heavy component removal through reduced pressure distillation in a light component removal tower and a heavy component removal tower in sequence to obtain a pure alkylbenzene product.
The molar ratio of benzene to long-chain olefin in step S1 is 1:2, the drying temperature of the dryer is 80 ℃.
Referring to fig. 2, in step S2, the alkylbenzene reactor is a fixed bed reactor, the novel catalyst is a mixture of a molecular sieve catalyst and a heat transfer catalytic fiber rod 1, and the mixing mass ratio is 1.
The molecular sieve catalyst adopts acidic centers formed by protonic acid or aprotic acid to be attached to the surface of a molecular sieve taking zeolite as a raw material, specifically, the protonic acid or the aprotic acid is used for carrying out saturation impregnation on the zeolite at the temperature of 30 ℃, then, dehydration drying is carried out at the temperature of 150 ℃, then, a nano magnetic iron oxide solution is taken for carrying out saturation impregnation at the temperature of 50 ℃, and finally, dehydration drying is carried out at the temperature of 80 ℃, so that the zeolite can be modified, high activity, high catalytic performance and certain magnetism are endowed to the zeolite, and the zeolite is used for being matched with the heat transfer catalytic fiber rod 1.
The mass ratio of the molecular sieve to the protonic acid or the non-protonic acid to the nano magnetic iron oxide solution is 1.
The molecular sieve catalyst accounts for 5% of the mass fraction of benzene and long-chain olefin.
Referring to fig. 3-7, a heat-transfer catalytic fiber rod 1 includes a heat-insulating fiber sleeve 11, an air-control ball 13 embedded in the center of the heat-insulating fiber sleeve 11, and a pair of heat-conducting wires 12 connected to the two ends of the inner side of the heat-insulating fiber sleeve 11, the outer end of the air-control ball 13 is connected with a pair of symmetrically distributed heat-insulating columns 14, one end of each heat-insulating column 14, which is far from the heat-insulating ball 15, is connected with a heat-insulating ball 15, the heat-insulating ball 15 is provided with a plurality of uniformly distributed heat-conducting holes, the heat-conducting magnetic balls 2 are movably embedded in the heat-conducting holes, the heat-conducting ball 15 is provided with a heat-conducting outer bag 3, the heat-conducting magnetic balls 2 are connected to the outer surface of the heat-conducting outer bag 3, the heat-conducting outer bag 3 extends into the air-control ball 13 through the heat-insulating columns 14, the outer end of the air-control ball 13 is embedded with a heat-conducting inner bag 4 corresponding to the heat-conducting wire 12, the heat-conducting inner bag 4 is communicated with the heat-conducting outer bag 3, the heat-transfer catalytic fiber rod 1 is filled between molecular sieve catalysts, the heat is absorbed by the heat-conducting magnetic ball 2, then the heat is transferred to the air control ball 13 through the heat-conducting outer bag 3, after the air control ball 13 is heated and expanded, on one hand, the heat-conducting mixture in the heat-conducting outer bag 3 is absorbed through the hydraulic suction force of the heat-conducting inner bag 4, the heat-conducting magnetic ball 2 is forced to migrate to the inside from the surface of the heat-insulating ball 15 along with the contraction of the heat-conducting outer bag 3, so that the absorption of the outside heat is reduced, at the moment, the heat-conducting inner bag 4 is contacted with the heat-conducting wire 12 under the expansion action of the air control ball 13 after absorbing the heat-conducting mixture, so that the heat-conducting connection is formed, the heat-conducting wire 12 transfers the heat on the heat-conducting outer bag 3 and the air control ball 13, so as to improve the heat transfer performance and the heat distribution uniformity inside the reactor, on the other hand, after the air control ball 13 is expanded, the reaction gas in the area can be extruded to the two sides, and just extruded into the inside of the molecular sieve catalyst to carry out sufficient gas-solid contact, therefore, the catalytic performance is effectively improved, the shape of the air control ball 13 is restored after the heat conducting wires 12 conduct away the heat, the heat conducting mixture in the heat conducting inner bag 4 returns to the heat conducting outer bag 3 after being extruded, the heat conducting magnetic ball 2 is reset at the same time to start absorbing a large amount of heat again, and the next round of extrusion is started, so that continuous expansion and contraction actions are formed.
The heat conduction oil and the heat conduction sand with the mass ratio of 1:1 are filled in the heat conduction outer bag 3, the part of the heat conduction outer bag 3 extending into the air control ball 13 and the heat conduction inner bag 4 are both in a compressed state, and the heat conduction oil and the heat conduction sand have good heat conductivity and have certain fluidity to migrate.
Referring to fig. 8, the heat-conducting magnetic ball 2 includes a heat-conducting casing 21 and a magnetic core ball 22 embedded in the heat-conducting casing 21, the heat-conducting casing 21 is made of a heat-conducting material, the magnetic core ball 22 is made of a ferromagnetic material, the heat-conducting casing 21 is used for absorbing heat and conducting the heat to the heat-conducting outer capsule 3, and the magnetic core ball 22 is used for magnetically attracting and matching with a molecular sieve catalyst, so that the heat-conducting magnetic ball 2 can be reset easily, and the heat conduction can be improved.
The heat insulation fiber sleeve 11, the heat insulation column 14 and the heat insulation ball 15 are all made of heat insulation materials, and the heat conduction magnetic ball 2 is made of thermal expansion materials.
Example 2:
referring to fig. 1-2, a novel catalytic process for the alkylation of aromatic amines with aromatics comprises the following steps:
s1, adding benzene and long-chain olefin into a dehydration tower in proportion, and after reflux dehydration, allowing the mixture to enter a dryer for drying treatment;
s2, heating the dried raw materials to 150 ℃ through a reaction heating furnace, and fully reacting in an alkylbenzene reactor under the catalysis of a novel catalyst to obtain a reaction product;
s3, allowing the reaction product to enter a debenzolization tower, distilling at normal pressure to remove unreacted benzene, and recycling;
and S4, removing light components and heavy components in the reaction product by subjecting the reaction product subjected to benzene removal to light component removal and heavy component removal sequentially through a light component removal tower and a heavy component removal tower, and obtaining a pure alkylbenzene product.
The molar ratio of benzene to long-chain olefin in step S1 is 1:2.2, the drying temperature of the dryer is 85 ℃.
Referring to fig. 3, in step S2, the alkylbenzene reactor is a fixed bed reactor, the novel catalyst is a mixture of a molecular sieve catalyst and a heat transfer catalytic fiber rod 1, and the mixing mass ratio is 1.
The mass ratio of the molecular sieve to the protonic acid or the non-protonic acid to the nano magnetic iron oxide solution is 1.
The molecular sieve catalyst accounts for 8 percent of the mass fraction of the benzene and the long-chain olefin.
The remainder was in accordance with example 1.
Example 3:
referring to fig. 1-2, a novel catalytic process for the alkylation of aromatic amines with aromatics comprises the following steps:
s1, adding benzene and long-chain olefin into a dehydration tower in proportion, and after reflux dehydration, drying in a dryer;
s2, heating the dried raw materials to 180 ℃ through a reaction heating furnace, and fully reacting in an alkylbenzene reactor under the catalysis of a novel catalyst to obtain a reaction product;
s3, allowing the reaction product to enter a debenzolization tower, distilling at normal pressure to remove unreacted benzene, and recycling;
and S4, removing light components and heavy components in the reaction product by subjecting the reaction product after benzene removal to light component removal and heavy component removal through reduced pressure distillation in a light component removal tower and a heavy component removal tower in sequence to obtain a pure alkylbenzene product.
The molar ratio of benzene to long-chain olefin in the step S1 is 1:2.5, the drying temperature of the dryer is 90 ℃.
Referring to fig. 3, in step S2, the alkylbenzene reactor is a fixed bed reactor, the novel catalyst is a mixture of a molecular sieve catalyst and a heat transfer catalytic fiber rod 1, and the mixing mass ratio is 1.
The mass ratio of the molecular sieve, the protonic acid or the aprotic acid and the nano magnetic iron oxide solution is 1.
The molecular sieve catalyst accounts for 10% of the mass fraction of benzene and long-chain olefin.
The remainder was in accordance with example 1.
The invention can realize that a novel catalyst is innovatively introduced on the basis of the existing production process, the novel catalyst comprises a molecular sieve catalyst and a heat transfer catalytic fiber rod 1, the molecular sieve catalyst adopts an acid center formed by protonic acid and non-protonic acid to be attached to the surface of a molecular sieve to form a catalyst with high activity and long service life, the catalyst is applied to a fixed bed reactor, the reaction process and the catalyst have no fluorine and chlorine, and can be recycled without backwashing, the introduced heat transfer catalytic fiber rod 1 can improve the problem of poor heat transfer performance in the fixed bed reactor, not only can the rapid heat transfer and uniform heat distribution be realized, but also the self expansion and contraction actions can be triggered by heat, so that the flow of reactant gas is caused in a local range, the catalytic reaction effect is improved by the contact of extrusion gas and the molecular sieve catalyst, and the efficient continuous production of alkylbenzene is realized.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (8)
1. A novel catalytic process for alkylating arylamine aromatic hydrocarbon is characterized in that: the method comprises the following steps:
s1, adding benzene and long-chain olefin into a dehydration tower in proportion, and after reflux dehydration, drying in a dryer;
s2, heating the dried raw materials to 130-180 ℃ through a reaction heating furnace, and fully reacting in an alkylbenzene reactor under the catalysis of a novel catalyst to obtain a reaction product;
s3, allowing the reaction product to enter a debenzolization tower, distilling at normal pressure to remove unreacted benzene, and recycling;
and S4, removing light components and heavy components in the reaction product by subjecting the reaction product after benzene removal to light component removal and heavy component removal through reduced pressure distillation in a light component removal tower and a heavy component removal tower in sequence to obtain a pure alkylbenzene product.
The alkylbenzene reactor is a fixed bed reactor in the step S2, the novel catalyst is a mixture of a molecular sieve catalyst and a heat transfer catalytic fiber rod (1), the mixing mass ratio is 1.5-0.8, the heat transfer catalytic fiber rod (1) comprises a heat insulation fiber sleeve (11), a gas control ball (13) embedded in the center of the heat insulation fiber sleeve (11) and a pair of heat conducting wires (12) connected to two ends of the inner side of the heat insulation fiber sleeve (11), the outer end of the gas control ball (13) is connected with a pair of heat insulation columns (14) which are symmetrically distributed, one end, away from the heat insulation ball (15), of each heat insulation column (14) is connected with the heat insulation ball (15), a plurality of heat conducting holes which are uniformly distributed are formed in the heat insulation ball (15), the heat conducting holes are movably embedded with matched heat conducting magnetic balls (2), an outer heat conducting bag (3) is arranged in each heat insulation ball (15), the plurality of heat conducting balls (2) are connected to the outer surface of the heat conducting outer heat conducting bag (3), the heat conducting outer heat conducting ball (3) penetrates through the heat insulation columns (14) and extends to the gas control ball (13), and the inner heat conducting wires (4) are connected with the heat conducting wires (4) correspondingly.
2. The novel catalytic process for the alkylation of aromatic amines with aromatic hydrocarbons according to claim 1, characterized in that: the molar ratio of benzene to long-chain olefin in the step S1 is 1:2-2.5, and the drying temperature of the dryer is 80-90 ℃.
3. The novel catalytic process for alkylation of arylamine aromatics according to claim 1, wherein: the molecular sieve catalyst adopts acidic centers formed by protonic acid or aprotic acid to be attached to the surface of a molecular sieve taking zeolite as a raw material, specifically, the protonic acid or the aprotic acid is used for carrying out saturated impregnation on the zeolite at the temperature of 20-80 ℃, then, dehydration and drying are carried out at the temperature of 80-250 ℃, then, the nano magnetic iron oxide solution is taken for carrying out saturated impregnation at the temperature of 20-60 ℃, and finally, dehydration and drying are carried out at the temperature of 80-120 ℃.
4. A novel catalytic process for the alkylation of aromatic amines with aromatics according to claim 3, characterized in that: the mass ratio of the molecular sieve, the protonic acid or the non-protonic acid and the nano magnetic iron oxide solution is 1.
5. A novel catalytic process for the alkylation of aromatic amines with aromatics according to claim 3, characterized in that: the molecular sieve catalyst accounts for 5-10% of the mass fraction of benzene and long-chain olefin.
6. The novel catalytic process for alkylation of arylamine aromatics according to claim 1, wherein: the heat conduction outer bag (3) is filled with heat conduction oil and heat conduction sand in a mass ratio of 1:1, and the part of the heat conduction outer bag (3) extending into the air control ball (13) and the heat conduction inner bag (4) are both in a compressed state.
7. The novel catalytic process for alkylation of arylamine aromatics according to claim 1, wherein: the heat conduction magnetic ball (2) comprises a heat conduction shell (21) and a magnetic core ball (22) embedded in the heat conduction shell (21), the heat conduction shell (21) is made of a heat conduction material, and the magnetic core ball (22) is made of a ferromagnetic material.
8. The novel catalytic process for alkylation of arylamine aromatics according to claim 1, wherein: the heat insulation fiber sleeve (11), the heat insulation column (14) and the heat insulation ball (15) are all made of heat insulation materials, and the heat conduction magnetic ball (2) is made of thermal expansion materials.
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| US5811623A (en) * | 1997-06-09 | 1998-09-22 | Catalytic Distillation Technologies | Isomerization of olefins by alkylation and dealkylation of aromatic hydrocarbons |
| CN1262282A (en) * | 1999-01-25 | 2000-08-09 | 中国石油化工集团公司 | Solid catalyst for polymerization of olefin and its preparing process |
| WO2008055122A1 (en) * | 2006-10-30 | 2008-05-08 | Uop Llc | Processes for producing alkylbenzenes over solid acid catalyst at low benzen to olefin ratios |
| CN111514924A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811623A (en) * | 1997-06-09 | 1998-09-22 | Catalytic Distillation Technologies | Isomerization of olefins by alkylation and dealkylation of aromatic hydrocarbons |
| CN1262282A (en) * | 1999-01-25 | 2000-08-09 | 中国石油化工集团公司 | Solid catalyst for polymerization of olefin and its preparing process |
| WO2008055122A1 (en) * | 2006-10-30 | 2008-05-08 | Uop Llc | Processes for producing alkylbenzenes over solid acid catalyst at low benzen to olefin ratios |
| CN111514924A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon |
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