CN116726939A - Supported catalyst for preparing acrylic acid by propylene oxidation and method for preparing acrylic acid by propylene oxidation - Google Patents
Supported catalyst for preparing acrylic acid by propylene oxidation and method for preparing acrylic acid by propylene oxidation Download PDFInfo
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- CN116726939A CN116726939A CN202111490682.5A CN202111490682A CN116726939A CN 116726939 A CN116726939 A CN 116726939A CN 202111490682 A CN202111490682 A CN 202111490682A CN 116726939 A CN116726939 A CN 116726939A
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- acrylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 38
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000007664 blowing Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 22
- 239000000428 dust Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical group [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 2
- 230000026676 system process Effects 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract 3
- 239000002245 particle Substances 0.000 description 34
- 239000000843 powder Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 19
- 239000003513 alkali Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010517 secondary reaction Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a supported catalyst for preparing acrylic acid by propylene oxidation and a method for preparing acrylic acid by propylene oxidation. The oxidation catalyst structure, the active ingredient and the blowing process provided by the invention are used for acrylic acid oxidation and waste combustion system processes thereof. The problems of deactivation of the waste combustion catalyst or reduction of the conversion rate of organic matters caused by dust falling off of the oxidation catalyst and blockage of the waste combustion catalyst by byproduct terephthalic acid (PTA) of the acrylic acid waste combustion system are solved from the two angles of a source and a process.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a metal honeycomb catalyst suitable for preparing acrylic acid by propylene oxidation, a method for preparing acrylic acid by propylene oxidation and a waste gas treatment process.
Background
Acrylic acid is an important petrochemical raw material, is generally widely used in the form of a synthetic intermediate, is mainly consumed in the form of a polymer, can be directly polymerized, and can be polymerized after acrylic ester is formed through esterification reaction. The most widespread use of acrylic acid today is in the production of thickeners, superabsorbent polymers, flocculants, builders and the like. In industry, the most important role of acrylic acid is to synthesize acrylic esters such as butyl acrylate, methyl acrylate, ethyl acrylate, etc. The acrylic ester products are mainly applied to the fields of paint, plastic modification auxiliary agents, rubber and the like. In a word, the acrylic acid and the ester have wide application range and large demand, and are important components in the petrochemical industry.
The standard for evaluating the quality of the catalyst in the acrylic acid oxidation reaction section is not only reflected in the quality of the product, but also the side reaction of the catalyst affects whether the catalyst is really suitable for actual production. Some high-boiling byproducts such as maleic acid, PTA and the like can block the subsequent equipment or the catalyst along with the flow of the reaction gas, so that the adverse effects of system pressure increase, catalyst activity reduction, yield reduction and the like are caused, and even the operation is influenced when serious, so that the device is stopped. For stable production in a long-term industrial scale, it is more desired to develop a catalyst which produces less side-reaction high-boiling substances. It has been studied that the addition of some other elements than the main active ingredient to the catalyst can reduce by-products of high boiling compounds, such as alkali metal elements (patent CN111757779 a) and by-products of aromatic compounds of high boiling compounds. However, it has been reported that a widely used particulate catalyst carrier is adopted, and the particulate catalyst is subjected to a tribological pulverization phenomenon in the actual operation process, and the produced catalyst powder also causes the rear end to be blocked.
The acrylic acid waste gas incinerator adopts a catalytic combustion treatment mode to convert organic waste gas into nontoxic and harmless gas, so that serious pollution to surrounding air is avoided. Along with the continuous improvement of domestic environmental protection indexes, the treatment requirements on waste gas devices are higher and higher, and the problems that the service life of the catalyst is lower than the expected service life because the surface of the catalyst is covered with a large amount of dust exist in the waste gas incineration devices of the domestic acrylic acid manufacturer at present, the waste gas incineration devices need to replace the waste combustion catalyst frequently, so that a great deal of financial resources and manpower resources are wasted. Taking acrylic acid and ester device of I's department as an example, every technological production parameter is in the normal range in the year that new catalyst is put into use, but find in work that its exhaust emission index is continuously rising, find after rigorous measurement that the total hydrocarbon content of non-methane has exceeded 200ppm, need to change new catalyst again and guarantee the environmental protection index. To meet the environmental protection requirement, the problem is solved.
Disclosure of Invention
The invention aims to solve the problem that the byproduct PTA produced in the preparation of acrylic acid by propylene oxidation blocks a rear end waste combustion system more highly, and provides a supported catalyst for preparing acrylic acid by propylene oxidation and a method for preparing acrylic acid by propylene oxidation.
At present, the acrylic acid oxidation catalyst at home and abroad mainly adopts spherical or cylindrical hollow bulk particles, continuously oscillates along with the change of air speed pressure in the operation process, and the surface active components fall off and are crushed by an internal structure, so that a large amount of dust enters an exhaust gas incineration system along with the process. Meanwhile, PTA particles which are byproducts of the oxidation reaction enter an exhaust gas incineration system along with gas. These dust and particles accumulate on the surface of the spent catalyst, causing catalyst pore plugging, reduced activity, and even deactivation. The prior art can not effectively solve the problems temporarily, and can only be stopped periodically to clean or replace a new catalyst, thereby influencing the operation period.
Therefore, the invention changes the existing structure and active ingredient composition of the acrylic acid oxidation section catalyst from the source, and reduces the catalyst dust and byproduct PTA. And the process is improved, and a blowing device is additionally arranged in front of the waste combustion system to intercept dust and PTA. In two aspects, the operation time of the waste combustion device is prolonged, and the waste combustion effect is improved.
A catalyst for preparing acrylic acid by propylene oxidation, which has a general formula:
Mo 12 V 4.5 Cu 2 A a B b Fe 2.2 O c ；
wherein Mo, V, cu, fe and O represent molybdenum, vanadium, copper, iron and oxygen, respectively;
a represents one or more of transition metal elements Sc, zn and Mn;
b represents one or more of rare earth elements La, pr and Nd;
a. b and c represent the atomic ratio of A, B to O;
a is 0.5 to 1, preferably 1;
b is 0.5 to 1, preferably 1;
c is a number determined by the oxidation state of each atom.
The PTA is mainly produced by deep oxidation of propylene in the catalyst due to overlong residence time and oxygen, and the addition of the transition metal element can effectively reduce the residence time of propylene in the catalyst, so that the PTA byproduct is reduced; the electron orbit transition of the outermost layer when the rare earth element is bonded can activate the bond energy of the main active components Mo and V of the catalyst to form a more stable crystal structure with the bond energy, so that the acting force among the metal elements in the catalyst is firmer, and the addition of the rare earth element can improve the stability of the catalyst and reduce the pulverization of the catalyst.
The precursor substances of each element of the catalyst active ingredient are as follows: mo is ammonium paramolybdate or molybdenum nitrate, V is ammonium metavanadate, cu is ammonium cuprate or copper nitrate, fe is ferric nitrate or ferrous nitrate, sc is scandium nitrate, zn is zinc nitrate, mn is manganese nitrate or ammonium homosulfate, la is lanthanum nitrate, pr is praseodymium nitrate, nd is neodymium nitrate.
The preparation method of the catalyst for preparing acrylic acid by propylene oxidation comprises the following steps: uniformly mixing precursor aqueous solutions of the active components of the catalyst, feeding by a peristaltic pump at a feeding rate of 7-15mL/min, atomizing the precursor aqueous solutions by compressed air with a pressure of 0.4-0.6MPa, uniformly spraying and attaching the atomized aqueous solutions to a metal honeycomb fixed carrier in an environment of 80-100 ℃, and drying at 200-300 ℃.
The metal honeycomb fixed carrier is a noble metal honeycomb cylindrical structure, as shown in figure 1, and the alumina carrier subjected to high-temperature stabilization treatment and the high-temperature-resistant corrosion-resistant alloy steel skeleton ensure that the whole catalyst is not easy to crush, and meanwhile, the catalyst has a stable specific surface area.
The appearance size of the metal honeycomb fixed carrier is r25×h400mm, and the opening ratio of the cross section is 280 meshes/square inch.
In the running process of the metal honeycomb fixed carrier, the highest temperature of a bed layer of the metal honeycomb fixed carrier cannot exceed 450 ℃, otherwise, the metal honeycomb fixed carrier is easy to crack. The metal honeycomb structure has lower resistance, so that in actual operation, the problem of local crushing of the catalyst caused by air inlet vibration and uneven pressure of propylene can be prevented. And, the honeycomb structure can increase the turbulence degree of the exhaust gas, so that the propylene and the air are oxidized uniformly as much as possible.
A method for preparing acrylic acid by propylene oxidation, which comprises the following steps: in the invention, two reactors for preparing acrylic acid by propylene oxidation are provided, namely, a conventional spherical Mo-Bi catalyst is reversely filled, the Mo-V catalyst is reversely filled, and molten salt is heated; the reaction temperature is 340-380 ℃, the reaction temperature is 250-320 ℃, and the propylene is as follows: air: the volumetric feed ratio of water vapor was 1: (2-10): (0.1-4), airspeed of 1000-2000h -1 。
The gaseous acrylic acid generated by the reaction is quenched and absorbed by desalted water through a quenching tower, and 55-60% of crude acrylic acid solution is generated in the tower kettle.
An acrylic acid tail gas treatment process comprises the following steps: one part of the unabsorbed gas from the top of the acrylic acid quenching tower is used as recycle gas to enter a reactor, and the other part of unabsorbed gas is used as tail gas to enter a waste burning system for catalytic burning through a blowing interception tank; the tail gas firstly passes through a heat exchanger 1, is preheated by hot gas after the waste combustion reaction, and then enters a heat exchanger 2 to be heated to the initial temperature of the waste combustion reaction; the tail gas enters a waste combustion reactor to convert organic matters such as propane, propylene and the like into carbon dioxide through catalytic oxidation; the hot gas after reaction generates steam through the heat exchanger 3, and then the tail gas entering the waste combustion system is preheated in the heat exchanger 1 by utilizing waste heat and is discharged.
The front end of the waste combustion system is additionally provided with a blowing interception tank, the top of the blowing interception tank is provided with a silk screen, and 16-27 blowing pipelines are horizontally arranged on the upper part of the silk screen and at a distance of 10-15cm from the top of the blowing interception tank. The compressed nitrogen is used as an air source, pulse blowing dust removal is intermittently carried out, solids attached to the surface of the silk screen are blown off, plugs fall to the bottom of the tank, and the plugs are discharged from the bottom along with condensate. The air injection adopts compressed nitrogen, the pressure is 0.5-0.7Mpa, the air inflow is set to 0.29-0.54% of the flow of the waste gas, and the air is injected at regular time every 15-30 minutes along the flow direction of the waste gas, so that the gas stability of the waste gas inlet device can be ensured.
Through the improvement of the catalyst structure and the active components and the optimization of the waste combustion process, the invention can reduce byproduct PTA particles and catalyst dust, effectively control the particles entering the waste combustion system, reduce the plugs on the surface of the waste combustion catalyst and prolong the operation period of the device.
Drawings
The preferred catalyst structure in the embodiment of fig. 1;
the preferred waste-fire system process in the embodiment of fig. 2;
the preferred blowing process configuration in the embodiment of fig. 3.
Detailed Description
Example 1
2118.62 g of ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 526.4 g of ammonium metavanadate (NH 4 VO 3 ) 376 g of copper nitrate (Cu (NO) 3 ) 2 ) 125.96 g of manganese nitrate (Mn (NO) 3 ) 2 ) 532.09 g of ferric nitrate (Fe (NO) 3 ) 3 ) 230.97 g scandium nitrate (Sc (NO) 3 ) 3 ) 326.92 g praseodymium nitrate (Pr (NO) 3 ) 2 ) Thoroughly mixed and stirred uniformly to prepare 68% aqueous solution.
Feeding by a feeding pump, wherein the feeding rate is 10mL/min, atomizing the powder by compressed air with the pressure of 0.6MPa, uniformly spraying the powder onto a metal honeycomb fixed carrier in an operation room at 80 ℃, and drying and forming the powder at 300 ℃. The size of the fixed carrier is r25 Xh 400mm, and the opening ratio of the cross section is 280 meshes/square inch. The prepared catalyst is integrally filled into a secondary reaction tube; a conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air: the volume feed ratio of the water vapor is 1:8:0.1, and the catalyst is contacted and reacted at a temperature of one reaction 375 ℃ and two reactions 280 ℃ with a space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) passing the reaction gas through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, blowing nitrogen once every 15min for 3 seconds, and collecting solid particles at the bottom of the tank after 48h for evaluating the quality of intercepted particles. The pressure of the injected nitrogen is 0.7Mpa, and the air inflow is set to 0.54% of the inflow of propylene and air.
The evaluation method comprises the following steps: 1) Weighing solid particles at the bottom of the collecting tank body, and evaluating the interception effect of the blowing system; 2) Placing the collected solid particles and the screen together in an alkali solution, wherein the acidic PTA is dissolved, the catalyst powder is insoluble in alkali, and evaluating the amount of PTA generated by alkali solution consumption; 3) And vertically placing the reaction tube filled with the two-way catalyst into an ultrasonic instrument, carrying out 60Hz ultrasonic treatment for 15 minutes, collecting dust particles falling from the lower part of the reaction tube, and weighing to evaluate the pulverization amount of the catalyst.
Example 2
2118.62 g of ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 526.4 g of ammonium metavanadate (NH 4 VO 3 ) 376 g of copper nitrate (Cu (NO) 3 ) 2 ) 125.96 g of manganese nitrate (Mn (NO) 3 ) 2 ) 532.09 g of ferric nitrate (Fe (NO) 3 ) 3 ) 184.78 g scandium nitrate (Sc (NO) 3 ) 3 ) 261.54 g praseodymium nitrate (Pr (NO) 3 ) 2 ) Thoroughly mixed and stirred uniformly to prepare 68% aqueous solution.
Feeding by a feeding pump, wherein the feeding rate is 10mL/min, atomizing the powder by compressed air with the pressure of 0.6MPa, uniformly spraying the powder onto a metal honeycomb fixed carrier in an operation room at 80 ℃, and drying and forming the powder at 300 ℃. The size of the fixed carrier is r25 Xh 400mm, and the opening ratio of the cross section is 280 meshes/square inch. The prepared catalyst is integrally filled into a secondary reaction tube; a conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air-conditioner: the volume feed ratio of the water vapor is 1:8:0.1, and the catalyst is contacted and reacted at a temperature of one reaction 375 ℃ and two reactions 280 ℃ with a space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) passing the reaction gas through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, blowing nitrogen once every 15min for 3 seconds, and collecting solid particles at the bottom of the tank after 48h for evaluating the quality of intercepted particles. The pressure of the injected nitrogen is 0.7Mpa, and the air inflow is set to 0.54% of the inflow of propylene and air.
The evaluation method comprises the following steps: 1) Weighing solid particles at the bottom of the collecting tank body, and evaluating the interception effect of the blowing system; 2) Placing the collected solid particles and the screen together in an alkali solution, wherein the acidic PTA is dissolved, the catalyst powder is insoluble in alkali, and evaluating the amount of PTA generated by alkali solution consumption; 3) And vertically placing the reaction tube filled with the two-way catalyst into an ultrasonic instrument, carrying out 60Hz ultrasonic treatment for 15 minutes, collecting dust particles falling from the lower part of the reaction tube, and weighing to evaluate the pulverization amount of the catalyst.
Example 3
2118.62 g of ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 526.4 g of ammonium metavanadate (NH 4 VO 3 ) 376 g of copper nitrate (Cu (NO) 3 ) 2 ) 125.96 g of manganese nitrate (Mn (NO) 3 ) 2 ) 532.09 g of ferric nitrate (Fe (NO) 3 ) 3 ) 115.49 g scandium nitrate (Sc (NO) 3 ) 3 ) 163.46 g praseodymium nitrate (Pr (NO) 3 ) 2 ) Thoroughly mixed and stirred uniformly to prepare 68% aqueous solution.
Feeding by a feeding pump, wherein the feeding rate is 10mL/min, atomizing the powder by compressed air with the pressure of 0.6MPa, uniformly spraying the powder onto a metal honeycomb fixed carrier in an operation room at 80 ℃, and drying and forming the powder at 300 ℃. The size of the fixed carrier is r25 Xh 400mm, and the opening ratio of the cross section is 280 meshes/square inch. The prepared catalyst is integrally filled into a secondary reaction tube; a conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air: the volume of the water vapor is increasedThe material ratio is 1:8:0.1, and the catalyst is contacted and reacted at a temperature of one reaction 375 ℃ and two reactions 280 ℃ with a space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) passing the reaction gas through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, blowing nitrogen once every 15min for 3 seconds, and collecting solid particles at the bottom of the tank after 48h for evaluating the quality of intercepted particles. The pressure of the injected nitrogen is 0.7Mpa, and the air inflow is set to 0.54% of the inflow of propylene and air.
The evaluation method comprises the following steps: 1) Weighing solid particles at the bottom of the collecting tank body, and evaluating the interception effect of the blowing system; 2) Placing the collected solid particles and the screen together in an alkali solution, wherein the acidic PTA is dissolved, the catalyst powder is insoluble in alkali, and evaluating the amount of PTA generated by alkali solution consumption; 3) And vertically placing the reaction tube filled with the two-way catalyst into an ultrasonic instrument, carrying out 60Hz ultrasonic treatment for 15 minutes, collecting dust particles falling from the lower part of the reaction tube, and weighing to evaluate the pulverization amount of the catalyst.
Comparative example 1
2118.62 g of ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 526.4 g of ammonium metavanadate (NH 4 VO 3 ) 376 g of copper nitrate (Cu (NO) 3 ) 2 ) 125.96 g of manganese nitrate (Mn (NO) 3 ) 2 ) 532.09 g of ferric nitrate (Fe (NO) 3 ) 3 ) 230.97 g scandium nitrate (Sc (NO) 3 ) 3 ) Thoroughly mixed and stirred uniformly to prepare 68% aqueous solution.
Feeding by a feeding pump, wherein the feeding rate is 10mL/min, atomizing the powder by compressed air with the pressure of 0.6MPa, uniformly spraying the powder onto a metal honeycomb fixed carrier in an operation room at 80 ℃, and drying and forming the powder at 300 ℃. The size of the fixed carrier is r25 Xh 400mm, and the opening ratio of the cross section is 280 meshes/square inch. The prepared catalyst is integrally filled into a secondary reaction tube; a conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air: the volume feed ratio of the water vapor is 1:8:0.1 volume feed ratio, strip at one reverse 375 ℃, two reverse 280 ℃Contact reaction with the catalyst under the part, and space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) passing the reaction gas through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, blowing nitrogen once every 15min for 3 seconds, and collecting solid particles at the bottom of the tank after 48h for evaluating the quality of intercepted particles. The pressure of the injected nitrogen is 0.7Mpa, and the air inflow is set to 0.54% of the inflow of propylene and air.
The evaluation method comprises the following steps: and vertically placing the reaction tube filled with the two-way catalyst into an ultrasonic instrument, carrying out 60Hz ultrasonic treatment for 15 minutes, collecting dust particles falling from the lower part of the reaction tube, and weighing to evaluate the pulverization amount of the catalyst.
Comparative example 2
2118.62 g of ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 526.4 g of ammonium metavanadate (NH 4 VO 3 ) 376 g of copper nitrate (Cu (NO) 3 ) 2 ) 125.96 g of manganese nitrate (Mn (NO) 3 ) 2 ) 532.09 g of ferric nitrate (Fe (NO) 3 ) 3 ) 326.92 g praseodymium nitrate (Pr (NO) 3 ) 2 ) Thoroughly mixed and stirred uniformly to prepare 68% aqueous solution.
Feeding by a feeding pump, wherein the feeding rate is 10mL/min, atomizing the powder by compressed air with the pressure of 0.6MPa, uniformly spraying the powder onto a metal honeycomb fixed carrier in an operation room at 80 ℃, and drying and forming the powder at 300 ℃. The size of the fixed carrier is r25 Xh 400mm, and the opening ratio of the cross section is 280 meshes/square inch. The prepared catalyst is integrally filled into a secondary reaction tube; a conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air: the volume feed ratio of the water vapor is 1:8:0.1, and the catalyst is contacted and reacted at a temperature of one reaction 375 ℃ and two reactions 280 ℃ with a space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) passing the reaction gas through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, blowing nitrogen once every 15min for 3 seconds, and collecting solid particles at the bottom of the tank after 48h for evaluating the quality of intercepted particles. The pressure of the injected nitrogen is 0.7Mpa, and the air inflow is set to 0.54% of the inflow of propylene and air.
The evaluation method comprises the following steps: collecting solid particles at the bottom of the tank body, putting the collected solid particles and a screen together into alkali liquor, wherein acidic PTA is dissolved, the catalyst powder is insoluble in alkali, and evaluating the amount of PTA generated by alkali liquor consumption.
Comparative example 3
The catalyst was charged in a conventional spherical Mo-V system catalyst (patent CN1031488A, example 1) which contained no transition metal element and no rare earth metal element. A conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air: the volume feed ratio of the water vapor is 1:8:0.1, and the catalyst is contacted and reacted at a temperature of one reaction 375 ℃ and two reactions 280 ℃ with a space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) passing the reaction gas through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, blowing nitrogen once every 15min for 3 seconds, and collecting solid particles at the bottom of the tank after 48h for evaluating the quality of intercepted particles. The pressure of the injected nitrogen is 0.7Mpa, and the air inflow is set to 0.54% of the inflow of propylene and air.
The evaluation method comprises the following steps: 1) Collecting solid particles at the bottom of the tank body, putting the collected solid particles and a screen together into alkali liquor, wherein acidic PTA is dissolved, catalyst powder is insoluble in alkali, and evaluating the amount of PTA generated by alkali liquor consumption; 2) And vertically placing the reaction tube filled with the two-way catalyst into an ultrasonic instrument, carrying out 60Hz ultrasonic treatment for 15 minutes, collecting dust particles falling from the lower part of the reaction tube, and weighing to evaluate the pulverization amount of the catalyst.
Comparative example 4
2118.62 g of ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 526.4 g of ammonium metavanadate (NH 4 VO 3 ) 376 g of copper nitrate (Cu (NO) 3 ) 2 ) 125.96 g of manganese nitrate (Mn (NO) 3 ) 2 ) 532.09 g of ferric nitrate (Fe (NO) 3 ) 3 ) 230.97 g of NitroScandium acid (Sc (NO) 3 ) 3 ) 326.92 g praseodymium nitrate (Pr (NO) 3 ) 2 ) Thoroughly mixed and stirred uniformly to prepare 68% aqueous solution.
Feeding by a feeding pump, wherein the feeding rate is 10mL/min, atomizing the powder by compressed air with the pressure of 0.6MPa, uniformly spraying the powder onto a metal honeycomb fixed carrier in an operation room at 80 ℃, and drying and forming the powder at 300 ℃. The size of the fixed carrier is r25 Xh 400mm, and the opening ratio of the cross section is 280 meshes/square inch. The prepared catalyst is integrally filled into a secondary reaction tube; a conventional spherical Mo-Bi based catalyst was reversely charged (patent CN103934000A, example 1).
Propylene is reacted with: air: the volume feed ratio of the water vapor is 1:8:0.1, and the catalyst is contacted and reacted at a temperature of one reaction 375 ℃ and two reactions 280 ℃ with a space velocity of 1500h -1 The reaction was carried out for 48 hours.
And (3) enabling the reaction generated gas to pass through a blowing interception tank, arranging 17 nitrogen blowing pipelines on the upper part of a silk screen and 10m away from the tank top, and collecting solid particles at the bottom of the tank body without starting blowing control.
The evaluation method comprises the following steps: solid particles at the bottom of the collecting tank body are weighed, and the interception effect of the blowing system is evaluated.
TABLE 1 catalyst composition and evaluation index
Claims (10)
1. A supported catalyst for preparing acrylic acid by propylene oxidation, which has a general formula:
Mo 12 V 4.5 Cu 2 A a B b Fe 2.2 O c ；
wherein Mo, V, cu, fe and O represent molybdenum, vanadium, copper, iron and oxygen, respectively;
a represents one or more of transition metal elements Sc, zn and Mn;
b represents one or more of rare earth elements La, pr and Nd;
a. b and c represent the atomic ratio of A, B to O;
a is 0.5 to 1, preferably 1;
b is 0.5 to 1, preferably 1;
c is a number determined by the oxidation state of each atom.
2. The supported catalyst according to claim 1, characterized in that the preparation method of the supported catalyst comprises the steps of: uniformly mixing precursor aqueous solutions of the active components of the catalyst, feeding by a peristaltic pump at a feeding rate of 7-15mL/min, atomizing the precursor aqueous solutions by compressed air with a pressure of 0.4-0.6MPa, uniformly spraying and attaching the atomized aqueous solutions to a metal honeycomb fixed carrier in an environment of 80-100 ℃, and drying at 200-300 ℃.
3. The supported catalyst according to claim 2, wherein the precursor substances of the respective elements of the catalyst active ingredient are: mo is ammonium paramolybdate or molybdenum nitrate, V is ammonium metavanadate, cu is ammonium cuprate or copper nitrate, fe is ferric nitrate or ferrous nitrate, sc is scandium nitrate, zn is zinc nitrate, mn is manganese nitrate or ammonium permanganate,
La is lanthanum nitrate, pr is praseodymium nitrate, and Nd is neodymium nitrate.
4. A method for preparing acrylic acid by propylene oxidation, which comprises the following steps: in two reactors for preparing acrylic acid by propylene oxidation, a catalyst of Mo-Bi series is reversely filled, the supported catalyst in claim 1 or 2 is reversely filled, the reaction temperature is 340-380 ℃, the reaction temperature is 250-320 ℃, and propylene is: air: the volumetric feed ratio of water vapor was 1: (2-10): (0.1-4), airspeed of 1000-2000h -1 。
5. The method of claim 4, further comprising an acrylic acid off-gas treatment process comprising the steps of: and (3) allowing one part of unabsorbed gas from the top of the acrylic acid quenching tower to enter the reactor as circulating gas, and allowing the other part of unabsorbed gas to enter a waste combustion system as tail gas through a blowing interception tank for catalytic incineration.
6. The method according to claim 5, wherein the tail gas subjected to catalytic incineration firstly passes through a heat exchanger (1), is preheated by hot gas after the waste combustion reaction, and then enters a heat exchanger (2) to be heated to the initial temperature of the waste combustion reaction; the tail gas enters a waste combustion reactor to be converted into carbon dioxide through catalytic oxidation; the hot gas after reaction generates steam through a heat exchanger (3), and then the waste heat is utilized to preheat the tail gas entering the waste combustion system in the heat exchanger (1) and then is discharged.
7. The method according to claim 5 or 6, wherein the top of the blowing interception tank is provided with a wire mesh, and 16-27 blowing lines are horizontally provided at a distance of 10-15cm from the top of the blowing interception tank above the wire mesh.
8. The method of claim 7, wherein the blowing line intermittently performs pulsed purge dust removal using compressed nitrogen as a gas source.
9. The method according to claim 8, characterized in that the nitrogen pressure is 0.5-0.7Mpa, and the intake air amount is set to 0.29-0.54% of the exhaust gas flow.
10. The method according to any one of claims 7-9, wherein the injection line is injected once every 15-30 minutes in the direction of the exhaust gas flow.
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