CN106866337B - Conversion and utilization process of mixed C4 - Google Patents
Conversion and utilization process of mixed C4 Download PDFInfo
- Publication number
- CN106866337B CN106866337B CN201510923693.6A CN201510923693A CN106866337B CN 106866337 B CN106866337 B CN 106866337B CN 201510923693 A CN201510923693 A CN 201510923693A CN 106866337 B CN106866337 B CN 106866337B
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- Prior art keywords
- utilization process
- oxidative dehydrogenation
- unit
- carbon
- conversion
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 title claims abstract description 137
- 230000008569 process Effects 0.000 title claims abstract description 119
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000003054 catalyst Substances 0.000 claims abstract description 150
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 135
- 238000006266 etherification reaction Methods 0.000 claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 95
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 claims abstract description 71
- 239000002994 raw material Substances 0.000 claims abstract description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 44
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- 238000002360 preparation method Methods 0.000 claims abstract description 32
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 20
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- 238000000926 separation method Methods 0.000 claims description 60
- 239000002243 precursor Substances 0.000 claims description 59
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 6
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 abstract description 16
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- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
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- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 4
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- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/8892—Manganese
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including oxidation as the refining step in the absence of hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
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Abstract
The invention provides a conversion and utilization process of mixed C4, which utilizes the mixed C4 to prepare high-octane gasoline components and butadiene. The process provided by the invention is characterized in that the raw material mixed carbon four sequentially passes through an oxidative dehydrogenation unit, an etherification unit and a catalytic dehydrogenation unit according to the characteristic that the content of n-butane, isobutane and olefin in the mixed carbon four is relatively rich, so as to obtain butadiene and a high-octane gasoline component. Meanwhile, the invention also provides a catalyst for preparing alkadiene by olefin oxidative dehydrogenation and a preparation method thereof. The mixed C-C conversion utilization process provided by the invention overcomes the defects that the conversion rate of tertiary carbon olefin, the high octane gasoline yield and the content of etherification products in gasoline are seriously influenced by diene, and simultaneously can produce a certain amount of high-value diene as a byproduct, thereby improving the economic benefit and the market competitiveness.
Description
Technical Field
The invention belongs to the technical field of oil refining, and particularly relates to a mixed carbon four conversion utilization process.
Background
In the twelfth five year, with the promotion of projects such as 2000 million tons/year oil refining of Guangdong petrochemical of China, 1000 million tons/year oil refining of Kunming, integrative engineering of four-Sichuan petrochemical refining, 80 million tons/year ethylene smoothening petrochemical, 120 million tons/year ethylene reconstruction and expansion of Daqing petrochemical and the like, the oil refining capacity and the ethylene capacity of the China petroleum are further expanded, and the yield of catalytic cracking C4 and cracking C4 resources which are byproducts of a refinery is also greatly increased. The C4 resource is mostly used as civil fuel to burn out except for part of MTBE, alkylate and polymer monomer. And C4 hydrocarbon and topped oil are not only low in price, but also high in transportation cost and large in loss in the transportation process, and belong to low-value products for refineries.
With the rapid development of national economy in China, the automobile holding capacity is continuously increased, and the demand for automobile fuel gasoline is increasingly large. Meanwhile, along with the increasing strictness of the environmental protection requirements on the gasoline quality standard, the quality standard of the motor gasoline is developing towards the direction of low sulfur content, low olefin content, low vapor pressure and high octane number. The market has great demands for increasing the yield of high-quality gasoline and blending components of low-sulfur low-olefin content high-octane gasoline, and the technical development in the aspect also becomes a hot problem concerned by various domestic research units and enterprises.
Butadiene is the main raw material of synthetic rubber, accounts for 71 percent of the total raw material, and the demand of butadiene reaches 350 ten thousand tons in 2015. The source of butadiene in China is single, a carbon four extraction method is mainly used, the butadiene is produced by an ethylene device, the total resource amount of the butadiene is 284-294 ten thousand tons calculated according to the ethylene capacity of 2100 ten thousand tons in 2015 year, and the butadiene has serious gaps. Another important source of butadiene is the technology of oxidative dehydrogenation of butenes. The butene oxidative dehydrogenation takes normal butene as a raw material, the domestic n-butene dehydrogenation catalyst is subjected to a ternary molybdenum catalyst, a six-membered molybdenum catalyst, an H-198 iron catalyst and a B-O2 iron catalyst under the joint efforts of domestic related units, and a reaction bed is also developed to a subsequent two-stage axial adiabatic fixed bed from an initial guide baffle fluidized bed. The industrial production proves that the combined process of the H-198 iron-based catalyst and the guide baffle fluidized bed and the combined process of the B-O2 iron-based catalyst and the two-section axial adiabatic fixed bed can greatly reduce the production cost and the environmental pollution of the domestic n-butene oxidative dehydrogenation device, and the comprehensive economic benefit reaches the advanced level at the same time.
however, since the 80 th century, with the continuous establishment of large-scale domestic ethylene plants, butadiene production process was gradually replaced by the lower-cost carbon four-extraction method, and many n-butene oxidative dehydrogenation plants were gradually stopped, so that the domestic n-butene oxidative dehydrogenation technology could not be further developed. However, in the long run, due to the influence of the light weight of raw materials of the ethylene cracking device, the new butadiene capacity of the extraction method is more and more difficult to meet the requirement of future downstream synthetic rubber on butadiene. From the production cost, the production cost of butadiene prepared by oxidative dehydrogenation of n-butene is 30-40% higher than that of the traditional extraction method.
on the other hand, with the building and expansion of more and more oil refining devices and ethylene devices, the production capacity of oil refining and ethylene in China is further expanded, and the yield of mixed carbon four resources such as catalytic cracking carbon four and cracking carbon four, which are byproducts of refineries, is also greatly increased. The carbon four resources are mostly used as civil fuel to be burnt except for part of the carbon four resources used for producing MTBE, alkylate, aromatized oil and polymerization monomer. The carbon four resources contain quite abundant n-butene and isobutene except n-butane and isobutane, and are very good raw materials for producing butadiene.
Phillips first developed a two-step n-butane dehydrogenation process to produce butadiene, the first step using a chromium-aluminum catalyst to dehydrogenate n-butane, and the second step further dehydrogenating n-butenes to butadiene in the presence of steam. The raw material of the method is only n-butane, and the method is not suitable for utilizing mixed carbon four generated in oil refining and chemical engineering processes.
In order to improve the product yield of butadiene prepared by dehydrogenating n-butane, BASF company continuously improves on the basis of Phillips two-step method technology, oxygen is added into a second-step dehydrogenation system to combine dehydrogenation reaction and oxidation reaction together, thereby greatly improving the conversion rate of n-butene and the selectivity of butadiene, and the process flow is as follows: a normal butane-containing feedstock is introduced into a first dehydrogenation zone and normal butane is catalytically dehydrogenated non-oxidatively to a first product gas stream of 1-butene, 2-butene and butadiene. The first product gas stream is introduced into a second dehydrogenation zone and 1-butene and 2-butene are oxidatively dehydrogenated to butadiene to produce a second product gas stream comprising butadiene, n-butane, etc., and butadiene is then recovered from the second product gas stream. The non-oxidative catalytic dehydrogenation of n-butane is carried out as autothermal catalytic dehydrogenation in a plate reactor comprising one or more continuous catalyst beds, the dehydrogenation catalyst being a platinum group catalyst. The catalyst for the oxidative dehydrogenation of n-butene to l, 3-butadiene is a molybdenum-bismuth-oxygen multimetal oxide system. Although the product yield of the two-step dehydrogenation process is greatly improved after oxygen is introduced, the process has multiple production steps, high cost and high steam consumption.
the company Snamprogetti SPA, italy, developed DET processes for the etherification of tertiary olefins in light gasolines, using its own tubular and tubular reactor technology, mainly consisting of: light gasoline separating tower, selective hydrogenation reactor, 2 etherification reactors, depentanizer, TAME separating tower, MPP adsorber and non-tertiary olefin skeletal isomerization reactor.
the TAME production process developed by French Petroleum Institute (IFP) includes raw material purification, etherification reaction and methanol recovery 3 parts. Except that the etherification reaction employs a main reactor (expanded bed reactor) and a final reactor (catalytic rectification column) in series, wherein 90% of the total feed is carried out in the expanded bed reactor.
a catalytic light gasoline etherification process developed by the Arco chemical technology company (ARCO) is mainly used for producing MTBE and co-producing TAME. The etherification reaction in the light gasoline etherification process adopts a series fixed bed adiabatic reactor. The technological process includes 3 unit processes of material purification, etherification reaction and methanol recovery. The C5 raw material is mixed with methanol after being washed and pretreated by selective hydrogenation, enters two fixed bed adiabatic reactors connected in series and reacts under the action of an ion exchange resin catalyst.
In patent CN103361113A, a method for producing high octane gasoline from a raw material rich in four carbon five carbon six is disclosed, in which the raw material rich in four carbon five carbon six is mixed with hydrogen to perform catalytic dehydrogenation reaction. The catalytic dehydrogenation product passes through a non-condensable gas separation device, after the non-condensable gas is separated out, the non-condensable gas is mixed with the raw material rich in olefin and hydrogen, the mixture enters an aromatization reactor to be contacted with an aromatization catalyst for aromatization reaction, and the product after the reaction can be separated into dry gas, liquefied gas, gasoline components and diesel oil components.
In patent CN103965002A, a method for oxidative dehydrogenation of low carbon hydrocarbons is disclosed, in which a low carbon hydrocarbon raw material, an oxygen-containing gas and a diluent are fed into a first stage reactor according to a certain proportion, the reacted material is mixed with a second low carbon hydrocarbon raw material and a second oxygen-containing gas, and then the mixture is fed into a next stage reactor, where the diluent comprises at least one of water vapor, N2, CO2, He or other inert gases.
Chinese patent CN102716754A discloses a preparation method of a catalyst for preparing butadiene by butylene oxidative dehydrogenation in a fluidized bed reactor, which comprises the steps of reacting a metal precursor and an alkaline substance at 10-90 ℃ and pH of 5-11 to obtain slurry containing insoluble compounds, filtering and washing the slurry to pH of 7-7.5, adding a proper amount of binder and deionized water, stirring, adjusting the solid content of the slurry to 10% -50%, spray drying and granulating the obtained slurry by spray drying and granulating equipment, drying the catalyst microspheres at a drying temperature of 200-400 ℃ and an outlet temperature of 100-160 ℃ to obtain catalyst microspheres, drying the catalyst microspheres at a drying temperature of 80-200 ℃ for 1-24h, roasting at 500-900 ℃ for 4-24h to obtain a catalyst finished product, wherein the obtained catalyst has a general formula of FeX a Y b Z c O56, wherein X is one or more than two of Ni, Co, Zn, Cu, Sn and Mn, Y is one or more than two of Bi, Mo, Cr, V, La, Zr, Ca, Sr and Ba, Z is one of Mg, Ba, Cu, Sn and Mn, Y is 0-1-6, Y is 0.1-6, the catalyst used for butadiene, the butadiene is used for normal pressure, the butadiene selectivity of the butadiene preparation is obtained by a, the butadiene preparation method after the butadiene preparation method, the butadiene catalyst finished product is used for a, the butadiene catalyst after the butadiene preparation method of the butadiene catalyst finished product is used for a, the butadiene preparation method of the butadiene catalyst is used for a butadiene catalyst for a, the butadiene preparation method of a butadiene catalyst for a butadiene preparation method.
CN1184705A discloses an iron-based catalyst for butadiene production by butylene oxidative dehydrogenation, which is composed of three or more divalent metal ions and Fe 3+, and has a general structural formula of a a 2+ B b 2+ C c 2+ Fe 2 O 4 · X (α -Fe 2 O 3), (when the general structural formula of the catalyst is Zn a Ca b -Co e Fe 2 O 4 · X (α -Fe 2 O 3), a ═ 0.8-0.9, a + B + C ═ 1, X ═ 15-65% (by weight), in a general formula of Zn a Ca 42 Co c Fe 2 O6862 · X (α -Fe 56O 3), a ═ 0.8-0.9, B ═ 0.03-0.08, a + B + C ═ 1, X ═ 20-40% (by weight)), where a is Zn, B is selected from Mg, B ═ 0.7, B ═ 0.70, B ═ 0.7, 0.10, 0.7-0.10, 0.7, 0.10, 10, 0.7, 10, 3, 10, 1, 10, 1, 10.
-1 -1CN103055890A discloses an iron catalyst for preparing butadiene by oxidative dehydrogenation of n-butene, which takes Fe as a main component, takes Mg, Zn and an extraction element as auxiliary agents, and has the mass composition of 48.80-60.53 wt% of Fe, 0.01-18.0 wt% of Mg, 0.0-15.0 wt% of Zn, and the total mass of other elements is 0.0-5.0 wt%, the balance is oxygen element, and the other elements are selected from one or more of Ba, Ca, Ni, Co, Cu, Cr, p, Si, Al, V, Ti, Mo, Sn, Sb, Zr, Mn, K and rare earth elements.
CN102824914A discloses a method for preparing butadiene by oxidative dehydrogenation of n-butene, which utilizes cobalt and magnesium elements to modify and prepare a zinc ferrite catalyst for the oxidative dehydrogenation of n-butene, but the catalyst is only suitable for n-butene, and the butadiene yield is only 77.8% at the highest under the conditions of 400-450 ℃ temperature, 1:4:16 volume ratio of raw material gas to air to steam, and 500- -1 butene volume space velocity, and the treatment capacity of the catalyst is also small.
CN101674883A discloses a zinc ferrite catalyst, which is difficult to achieve ideal catalytic effect by simple zinc ferrite combination, and the catalyst is used in a fixed bed reactor, the temperature rise of the catalyst bed is serious, the energy consumption is high, and the problem of abrasion of the catalyst on a fluidized bed reactor can not be solved.
US patents 3450788 and US3450787 disclose a number of different spinel structure iron chromate butene oxidative dehydrogenation catalysts. The spinel iron chromate catalyst has good reaction performance for preparing butadiene through oxidative dehydrogenation of butene, the one-way molar conversion rate of the butene is 70%, and the highest molar selectivity of the butadiene is 92%.
CN1033013A, CN101674883A, CN1184705A and the like disclose preparation methods of ferrite-based catalysts for preparing butadiene by oxidative dehydrogenation of butene. The molar conversion of butene on these catalysts is generally from 70 to 80% and the molar selectivity to butadiene from 89 to 93%. Some of these patents have been used industrially in China, but are limited by the demand and process level of butadiene at that time, and are forced to stop production.
Disclosure of Invention
in order to overcome the problems, the invention aims to provide a mixed carbon four conversion and utilization process. The technical scheme provided by the invention aims at the composition characteristic that the mixed C4 contains relatively rich n-isobutane and n-isoolefin, and provides a process for producing butadiene and high-octane gasoline components by mainly combining oxidative dehydrogenation, etherification and catalytic dehydrogenation of the mixed C4.
in order to achieve the purpose, the invention provides a mixed carbon four conversion and utilization process, which at least comprises the following steps:
The first step is as follows: sending the mixed C-C raw material, a material flow containing an oxidant and water or steam into an oxidative dehydrogenation unit for alkane oxidative dehydrogenation reaction, and sending a reaction product into a separation unit I for separation into butadiene, other C-C fractions except the butadiene and the rest components; the second step is that: feeding the other carbon four fractions except butadiene obtained in the first step and alcohol material flow into an etherification unit for etherification reaction, and feeding reaction products into a separation unit II for separation into five-carbon and above components, four-carbon hydrocarbons and residual components; the third step: feeding the carbon tetrahydrocarbon and hydrogen obtained in the second step into a catalytic dehydrogenation unit for alkane catalytic dehydrogenation reaction, feeding a reaction product into a separation unit III for separation into noncondensable gas and residual components, and returning the residual components to the oxidative dehydrogenation unit in the first step; in the first step, the oxidative dehydrogenation catalyst used is of formula (I):
A a B b C c D d. Fe x O e formula (I)
In formula (I): a is Cu, Zn or Cr; b is Co, Mn, Ni or Mo; c is Ca, Sr, Ba or Mg; a is 1-6, b is 0.01-0.3, c is 0.1-1.0, d is 0.01-0.1, x is 4-18, and e is any value meeting the valence requirement.
in the process of producing butadiene by using the two-step dehydrogenation method, n-butene and n-butane are mainly contributed, so that the conversion rate of isobutene and isobutane is low. And in the catalytic dehydrogenation process, the conversion rate of converting isobutane into isobutene is high. The etherification technology can be used for converting tertiary carbon olefin in the material flow into corresponding ether compounds under the action of the catalyst, the conversion rate of the tertiary carbon olefin is over 95 percent, and isobutene is converted into the ether compounds with high octane number to be used as gasoline blending components. Different from n-butene and n-butane raw materials, the mixed C4 contains rich n-butane and also contains n-butene, isobutene and isobutane with equivalent content.
In the above-described mixed carbon four conversion utilization process, preferably, in formula (I): a is 3-5, b is 0.05-0.15, c is 0.3-0.6, d is 0.04-0.08, and x is 7-13.
The percentages not specifically described in the present invention are mass percentages.
In the above-mentioned mixed carbon four conversion utilization process, the mixed carbon four raw material includes carbon four hydrocarbons produced in the oil refining and chemical industry process, such as ether carbon four, catalytic cracking carbon four, and also can be the separation component of light gasoline. Preferably, the content of the C-tetracarbon in the mixed C-four raw material is not less than 95% by mass, and preferably not less than 99% by mass; the mass content of the carbon tetraolefin is not less than 40 percent, preferably not less than 50 percent; the mass sum of the n-butene and n-butane is not less than 35%, preferably not less than 40%. Can be raw materials from the same source or can be mixed with raw materials from different sources.
In the above mixed C-C conversion utilization process, preferably, the reaction conditions of the oxidative dehydrogenation unit are that the temperature is 280-410 ℃, preferably 310-390 ℃, the pressure is 0-100KPa, preferably 0-40KPa, and the volume space velocity is 10-500h -1, preferably 60-400h -1.
the space velocities not specifically described in the present invention are all liquid hourly volume space velocities.
in the above mixed C4 conversion utilization process, the stream containing oxidant in the oxidative dehydrogenation unit in the third step may be a stream containing oxygen molecules or oxygen atoms with strong oxidizability, such as oxygen, oxygen-rich gas, air, etc.; preferably air, oxygen-rich gas and oxygen; further preferably oxygen-rich; more preferably oxygen-enriched gas with an oxygen content between 32% and 45%. Wherein the molar ratio of oxygen to olefin in all hydrocarbon feed entering the oxidative dehydrogenation unit is 0.1-1.0:1, preferably 0.3-0.85:1, calculated as oxygen in the oxidant-containing stream. In the feeding process of the oxidative dehydrogenation unit, water or steam with a certain ratio is added, so that the problems of coking of the catalyst and over-quick temperature rise of a catalyst bed layer caused by coking can be prevented. The mass ratio of water or steam to all hydrocarbon feed to the oxydehydrogenation unit can be from 0.5 to 30:1, preferably from 5 to 20: 1.
in the above mixed C4 conversion utilization process, the reactor of the oxidative dehydrogenation unit comprises a fluidized bed reactor or a fixed bed reactor, preferably a fluidized bed reactor; the reactor can be operated in a single batch mode, and also can be operated in a mode that two or more reactors are connected in series or/and in parallel.
in the above-mentioned mixed C4 conversion and utilization process, the separation method in the separation unit I may be extraction, rectification, extractive distillation, azeotropic distillation, membrane separation, chemical absorption, or the like. And selecting a separation technology with a mature technology to obtain a qualified butadiene product, wherein the mass content of butadiene in the separated carbon four-fraction except butadiene is not higher than 0.3%, and preferably not higher than 0.1%.
in the above mixed carbon four conversion utilization process, preferably, the alcohol stream in the etherification unit is a lower alcohol with a carbon number of not more than 4, preferably methanol, ethanol, more preferably methanol.
In the above-described mixed C4 conversion utilization process, it is preferred that the molar ratio of the alcohols to isobutylene in all hydrocarbon feeds to the etherification unit is from 0.8 to 1.5:1, preferably from 1.1 to 1.3:1, upon entry into the etherification unit.
In the above-mentioned mixed C-C conversion utilization process, the reaction conditions of the etherification unit are preferably 30-100 deg.C, preferably 45-80 deg.C, pressure 0.1-2.0MPa, preferably 0.5-1.5MPa, and volume space velocity 0.1-5h -1, preferably 1-2h -1.
In the above-mentioned mixed carbon-four conversion utilization process, the etherification catalyst is not particularly limited in the etherification unit, and preferably, the conversion of isobutylene is not less than 92%, preferably not less than 95%.
In the above mixed C4 conversion and utilization process, the etherification reactor is not particularly limited, and may be one or a combination of several of a fixed bed, a moving bed suspension bed, a catalytic distillation reactor, and the like. But preferably adopts a catalytic distillation technology, tertiary carbon olefin can be fully converted, the four-carbon fraction produced at the top of the dealcoholization tower in the separation unit is sent to a catalytic dehydrogenation unit, the gasoline component with high octane number produced at the bottom of the tower can be used, and the recovered alcohol can also be recycled to the inlet of the etherification reactor for use.
In the above mixed carbon four conversion utilization process, the separation method in the separation unit II is not limited, and may be rectification, extraction, membrane separation, or the like, but rectification is preferably used. Preferably, the mass content of the carbon four component in the separated carbon four hydrocarbon is not less than 97%, preferably not less than 99%.
In the above-described mixed carbon-four conversion utilization process, the dehydrogenation catalyst is not particularly limited in the catalytic dehydrogenation unit, and preferably, the catalytic dehydrogenation product has an olefin content of not less than 35% by mass, and preferably an olefin content of not less than 45% by mass.
In the above mixed C-C conversion utilization process, the reaction conditions of the catalytic dehydrogenation unit are 480-700 ℃, 0.01-3MPa, and 0.1-10h -1, and more preferably, the reaction conditions of the catalytic dehydrogenation unit are 560-650 ℃, 0.4-1.2MPa, and 2-7h -1.
In the above-mentioned mixed C4 conversion utilization process, when entering the catalytic dehydrogenation unit, the molar ratio of hydrogen to all hydrocarbon materials entering the catalytic dehydrogenation unit is 0.01-1:1, preferably 0.1-0.5: 1.
In the above mixed C4 conversion utilization process, the catalytic dehydrogenation reactor is preferably a fixed bed reactor, and may be one reactor used alone, intermittently realized through two processes of reaction-catalyst regeneration, or two or more reactors used in parallel for cyclic operation, or a plurality of reactors used in parallel and/or in series. When the catalyst in one or more reactors is seriously inactivated due to carbon deposition, the inactivated catalyst is recycled after regeneration by switching the material inlet and the material outlet, and the continuous operation of a reaction and regeneration system is realized.
In the above mixed carbon four conversion utilization process, preferably, the non-condensable gas separated by the separation unit III and the dry gas (methane, ethane propane) separated by the separation unit II may be directly recycled to the material inlet of the catalytic dehydrogenation unit for recycling.
in the above mixed carbon-four conversion utilization process, preferably, the separation unit may include a separation device for non-condensable gas, such as a flash tank, an absorption/desorption tower, a cooling device, a compression device and the like.
-1 -1 -1 -1In the above-mentioned process for converting and utilizing mixed C-C, the invention provides a preferred embodiment, a mixed C-C raw material is used, the mass content of C-C is not less than 95%, preferably not less than 99%, the mass content of C-C.
in the above mixed carbon-four conversion utilization process, preferably, the preparation process of the oxidative dehydrogenation catalyst used in the oxidative dehydrogenation unit includes at least the following steps:
(1) respectively grinding precursors of the used metals A, B, C and D into microspheres with 40-100 meshes; dividing the grinded precursor of the metal A into two parts by weight; simultaneously, uniformly mixing precursors of the metal B, C and the D;
(2) Preparing 0.1-2mol/L ferric nitrate solution, gradually adding a first part of precursor of metal A into the ferric nitrate solution under the condition of stirring, reacting for 30-90 minutes, adding the precursor of metal B, C and D which are uniformly mixed, continuing to react for 30-90 minutes, adding a second part of precursor of metal A, continuing to react for 20-80 minutes, and adding a binder to obtain slurry of precursor precipitate;
(3) Stirring the slurry obtained in the step (2) for 20-60 minutes, and gradually adding ammonia water with the concentration of 10-25% into the slurry to adjust the pH value of the slurry to 7.5-10;
(4) Placing the slurry after the pH is adjusted in the step (3) in an environment of 80-95 ℃ for thermal modification, wherein the modification time is 60-180 minutes;
(5) Filtering the modified slurry obtained in the step (4), washing with washing water to enable the pH value of the slurry to reach 7-7.5, adjusting the solid content of the slurry to be 5-40%, then performing spray forming, and roasting at 400-500 ℃ for 6-12 hours to obtain a finished catalyst;
or filtering the modified slurry in the step (4), washing with washing water, and enabling the pH value of the slurry to reach 7-7.5, then roasting at 100-200 ℃ for 6-12 hours, at 200-300 ℃ for 4-8 hours, at 300-400 ℃ for 1-4 hours, at 400-500 ℃ for 1-4 hours, and grinding to obtain the finished catalyst.
in the above method for preparing the oxidative dehydrogenation catalyst, preferably, the first part of the metal a precursor in the step (1) is 55 to 70% of the total weight of the metal a precursor.
In the above-mentioned preparation method of the oxidative dehydrogenation catalyst, preferably, the precursors of the metals A, B, C and D in step (1) are respectively selected from one or a combination of several of nitrates, chlorides, sulfates and oxides of the corresponding metals.
In the above preparation method of the oxidative dehydrogenation catalyst, preferably, the binder in step (2) comprises one or a combination of several of sesbania powder, polyacrylamide, methylcellulose and polyvinyl alcohol; further preferably, the addition amount of the binder is 0.1 to 4%, preferably 1 to 2%, of the total mass of the metal precursor.
in the above-mentioned method for producing an oxidative dehydrogenation catalyst, it is preferable that the pH of the slurry in the step (3) is adjusted to 8.0 to 9.0.
In the above-mentioned method for producing an oxidative dehydrogenation catalyst, it is preferable that the concentration of the iron nitrate solution of the step (2) is 0.3 to 1.0 mol/L.
In the above-mentioned method for producing an oxidative dehydrogenation catalyst, it is preferable that the binder is added in step (2) after reacting for 40 to 60 minutes.
In the above-mentioned method for producing an oxidative dehydrogenation catalyst, it is preferable that the modification time of the slurry after the completion of the pH adjustment in step (4) is 90 to 120 minutes.
In the preparation method of the oxidative dehydrogenation catalyst, preferably, the spray forming is preferably completed by using a spray tower, the feeding temperature of the spray tower is preferably 300-500 ℃, and the discharge temperature is preferably 100-150 ℃.
In the above-mentioned method for preparing an oxidative dehydrogenation catalyst, preferably, the washing water in the step (5) may be one or more of deionized water, distilled water, desalted water and tap water.
The conversion and utilization process of mixed C4 provided by the invention has the advantages that in the process of modifying and utilizing mixed C4, the defects that the production process of the isomerization technology is not friendly to the environment, the generation rate of dry gas of the high-temperature aromatization technology is higher than 20% at all times, the economic benefit of the process is not slightly lost and the like are overcome, in the process of continuously and deeply researching and utilizing the etherification technology, the problems that the conversion rate of mono-olefin etherification and the yield of ether compounds are seriously influenced by the diene and a certain amount of high-value diene can be produced as a byproduct are solved by adding the diene separation unit and the diene unit in the process of oxidizing dehydrogenation production, so that the economic benefit and market competitiveness of the process are improved, and another process is provided for more finely utilizing low-carbon alkanes. In addition, during the oxidative dehydrogenation, small amounts of ketones and aldehydes are produced due to the occurrence of side reactions. If the aldehyde and ketone are produced in too high an amount, not only is the diene selectivity directly affected, but also the process costs are increased by treating the waste water from washing the aldehyde and ketone. In the scheme provided by the invention, a special olefin oxidative dehydrogenation catalyst is adopted, and particularly, the catalyst preparation method recommended by the invention is adopted, firstly, the metal precursor is ground, and the metal precursor A is added step by step according to the weight parts of 55-70% and 30-45%; pre-mixing the metal precursor B, C and D uniformly; can ensure that each active component can be uniformly nucleated in the preparation process of the catalyst, and improve the stability of the catalyst; in addition, the catalyst is added with the tungsten serving as an oxidizing agent in the preparation process, so that the activity of the catalyst can be effectively improved. The total amount of the materials entering the reaction system is controlled by controlling the oxygen content in the oxygen-enriched air flow, so that the contact of oxygen atoms and olefin in the reaction system with the catalyst is controlled, and the reaction residence time is controlled from the other aspect. The adoption of said process not only can ensure that the monoolefine can be fully converted into diolefin, but also can effectively control the production of alcohols and aldehydes, and can raise the yield and selectivity of diolefin.
drawings
FIG. 1 is a schematic process flow diagram of examples 9-16 and comparative example 3.
In fig. 1: r1 is an oxidative dehydrogenation reactor, R2 is an etherification dehydrogenation reactor, R3 is a catalytic oxidation reactor, and T1, T2 and T3 respectively correspond to a separation system I, a separation system II and a separation system III.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
tables 1 and 2 show properties of the mixed carbon four raw material used in the examples, mixed carbon four a is catalytic shop mixed carbon four of lanzhou petrochemical company, and mixed carbon four B is one-heavy catalytic mixed carbon four of daqing refinery company. The methanol is the methanol produced by Cangzhou Zhengyuan chemical industry limited company, wherein the mass content of the methanol is 99.5 percent. The ethanol is anhydrous ethanol produced by autumn cloud chemical limited company in Yixing city, wherein the mass content of the ethanol is 99.5%.
The processes shown in the figure 1 are adopted in the examples 9 to 16 and the comparative example 3, and the catalytic dehydrogenation reactors in the examples are 200ml pressurized fixed bed reactors which are used in a circulating manner; the oxidative dehydrogenation units used in examples 9 and 14 were 100ml fixed bed reactors, and the oxidative dehydrogenation units used in examples 10 to 13 were 100ml fluidized bed reactors; the etherification reaction system in each example adopts a catalytic distillation reaction device, the pre-etherification reactor is a 200ml fixed bed, and the catalyst loading in the reactive distillation tower is 150 ml. The samples analyzed were transient samples after 3 hours of reaction. A rectification column having a theoretical plate number of 18 was used in separation unit I (T1). And (3) dehydrating in a separation unit II (T2) by adopting a cyclone separator, removing non-condensable gas by flash evaporation, and separating the dialkene by an extraction method. The separation unit III (T3) used a rectification column with a theoretical plate number of 10.
In the raw materials for preparing the catalyst in the examples, sesbania powder is industrial grade, and the others are all commercial chemical pure reagents.
The water is deionized distilled water.
The oxygen-enriched air flow is prepared by mixing industrial-grade pure oxygen and air.
In the examples, the method for calculating the olefin content, the diene mass yield and the etherification product yield is as follows:
The content of olefins is the mass of butenes, pentenes produced in the catalytic dehydrogenation product/mass of all hydrocarbons in the catalytic dehydrogenation product x 100;
the mass yield of the alcohols is equal to the mass of the alcohols produced by the oxidative dehydrogenation unit and/or the mass of the hydrocarbon material entering the oxidative dehydrogenation unit x 100;
The mass yield of the ketones is equal to the mass of the ketones generated by the oxidative dehydrogenation unit and/or the mass of the hydrocarbon material entering the oxidative dehydrogenation unit x 100;
The mass yield of the diolefin is equal to the mass of the diolefin generated by the oxidative dehydrogenation unit/the mass of the hydrocarbon material entering the oxidative dehydrogenation unit multiplied by 100;
The yield of the etherification product is the mass of all the products subjected to etherification after the removal of the non-condensable gas/the mass of the hydrocarbon material entering the etherification unit multiplied by 100.
TABLE 1 composition of C4A blends (w%)
| Components | w％ | Components | w％ |
| Propane | 0.04 | Isobutene | 17.11 |
| Propylene (PA) | 0.01 | Cis-butene-2 | 12.51 |
| isobutane | 24.50 | Isopentane | 0.66 |
| N-butane | 14.16 | 1, 3-butadiene | 0.09 |
| trans-butene-2 | 17.51 | 2-methyl-2-butene | 0.01 |
| 1-butene | 13.39 | 1-pentene | 0.01 |
TABLE 2 composition of C-C B mixture (w%)
| Components | w％ | Components | w％ |
| propane | 0.00 | Isobutene | 12.45 |
| Propylene (PA) | 0.00 | Cis-butene-2 | 12.79 |
| Isobutane | 34.29 | Isopentane | 0.06 |
| N-butane | 10.38 | 1, 3-butadiene | 0.07 |
| trans-butene-2 | 17.33 | 2-methyl-2-butene | 0.02 |
| 1-butene | 12.63 | 1-pentene | 0.04 |
Example 1
This example provides an oxidative dehydrogenation catalyst, the specific preparation process of which comprises the following steps:
(1) firstly, 1785g of zinc nitrate hexahydrate serving as a precursor of metal A, 90g of nickel nitrate hexahydrate serving as a precursor of B, 197.1g of calcium chloride hexahydrate serving as a precursor of C and 5g of tungsten trioxide serving as a precursor of D are ground into a microspherical shape with a mesh size of 50 meshes; secondly, dividing zinc nitrate hexahydrate into 1071g and 714g according to the proportion of 60 percent and 40 percent, and uniformly mixing nickel nitrate hexahydrate, calcium chloride hexahydrate and tungsten trioxide;
(2) Preparing 8.5L of 2mol/L ferric nitrate solution, under the stirring condition, firstly, gradually adding 1071g of zinc nitrate hexahydrate into the ferric nitrate solution, reacting for 70 minutes, then slowly adding a mixture of nickel nitrate hexahydrate, calcium chloride hexahydrate and tungsten trioxide, reacting for 90 minutes, then slowly adding 714g of zinc nitrate hexahydrate, reacting for 50 minutes, and then adding 36g of binder methyl cellulose to obtain slurry of precursor precipitate;
(3) Stirring the slurry obtained in the step (2) for 20 minutes, and gradually adding ammonia water with the concentration of 25% into the slurry to adjust the pH value of the slurry to 8.0;
(4) Placing the slurry after the pH is adjusted in the step (3) in an environment of 85 ℃ for thermal modification, wherein the modification time is 180 minutes;
(5) filtering the modified slurry in the step (4), washing with tap water and distilled water to enable the pH value of the slurry to reach 7.2, roasting and modifying a filter cake at 200 ℃ for 12 hours, roasting and modifying at 300 ℃ for 4 hours, roasting and modifying at 400 ℃ for 4 hours, cooling, grinding, and screening out catalyst microspheres with 60-100 meshes to obtain the finished catalyst mainly comprising Zn 6 Ni 0.3 Ca 0.9 W 0.02. Fe 17 O 32.7.
example 2
This example provides an oxidative dehydrogenation catalyst, the specific preparation process of which comprises the following steps:
(1) firstly, 622.5g of precursor copper nitrate of metal A, 116.4g of precursor cobalt nitrate hexahydrate of B, 20.8g of precursor barium chloride of C and 12g of precursor tungsten trioxide of D are ground into a microspherical shape with 70 meshes; secondly, dividing copper nitrate into 404.6g and 217.9g according to the proportion of 65% and 35%, and uniformly mixing cobalt nitrate hexahydrate, barium chloride and tungsten trioxide;
(2) Preparing 36L of 0.5mol/L ferric nitrate solution, gradually adding 404.6g of copper nitrate into the ferric nitrate solution under the stirring condition, reacting for 60 minutes, slowly adding a mixture of nickel nitrate hexahydrate, calcium chloride hexahydrate and tungsten trioxide, reacting for 70 minutes, slowly adding 217.9g of copper nitrate, reacting for 50 minutes, and adding 0.8g of binder methyl cellulose to obtain a slurry of a precursor precipitate;
(3) Stirring the slurry obtained in the step (2) for 30 minutes, and gradually adding ammonia water with the concentration of 20% into the slurry to adjust the pH value of the slurry to 8.5;
(4) placing the slurry after the pH is adjusted in the step (3) in an environment of 80 ℃ for thermal modification, wherein the modification time is 90 minutes;
(5) And (3) filtering the modified slurry obtained in the step (4), washing with tap water to enable the pH value of the slurry to reach 7.5, adjusting the solid content to be 20%, enabling the slurry to pass through a spray forming tower, controlling the inlet temperature to be 380 ℃ and the outlet temperature to be 130 ℃, and roasting and modifying the slurry at 400 ℃ for 12 hours to obtain the finished product catalyst mainly comprising Cu 2.5 Co 0.4 Ba 0.1 W 0.06. Fe 18 O 30.2.
example 3
this example provides an oxidative dehydrogenation catalyst, the specific preparation process of which comprises the following steps:
(1) firstly, 297.5g of zinc nitrate hexahydrate serving as a precursor of metal A, 25.4g of manganese sulfate monohydrate serving as a precursor of B, 266g of strontium chloride hexahydrate serving as a precursor of C and 13.9g of tungsten trioxide serving as a precursor of D are ground into microspheres of 40 meshes; secondly, dividing zinc nitrate hexahydrate into 208.3g and 89.2g according to the proportion of 70% and 30%, and uniformly mixing manganese sulfate monohydrate, strontium chloride hexahydrate and tungsten trioxide;
(2) Preparing 10L of 0.7mol/L ferric nitrate solution, under the stirring condition, firstly, gradually adding 208.3g of zinc nitrate hexahydrate into the ferric nitrate solution, reacting for 30 minutes, then slowly adding a mixture of manganese sulfate monohydrate, strontium chloride hexahydrate and tungsten trioxide, reacting for 90 minutes, then slowly adding 89.2g of zinc nitrate hexahydrate, reacting for 40 minutes, and then adding 13.9g of binder methyl cellulose to obtain slurry of precursor precipitates;
(3) stirring the slurry obtained in the step (2) for 50 minutes, and gradually adding 25% ammonia water into the slurry to adjust the pH value of the slurry to 10.0;
(4) Placing the slurry after the pH is adjusted in the step (3) in an environment of 85 ℃ for thermal modification, wherein the modification time is 100 minutes;
(5) and (3) filtering the modified slurry obtained in the step (4), washing with deionized water to enable the pH value of the slurry to reach 7.0, adjusting the solid content to 35%, enabling the slurry to pass through a spray forming tower, controlling the inlet temperature to be 500 ℃ and the outlet temperature to be 150 ℃, and roasting and modifying the slurry at 450 ℃ for 10 hours to obtain the finished catalyst mainly comprising Zn 1 Mn 0.15 Sr 1 W 0.06. Fe 7 O 12.8.
example 4
this example provides an oxidative dehydrogenation catalyst, the specific preparation process of which comprises the following steps:
(1) firstly, 1785g of zinc nitrate hexahydrate serving as a precursor of metal A, 14.9g of nickel nitrate hexahydrate serving as a precursor of B, 21.9g of calcium chloride hexahydrate serving as a precursor of C and 23.1g of tungsten trioxide serving as a precursor of D are ground into a microspherical shape with a mesh size of 50 meshes; secondly, dividing zinc nitrate hexahydrate into 1071g and 714g according to the proportion of 60 percent and 40 percent, and uniformly mixing nickel nitrate hexahydrate, calcium chloride hexahydrate and tungsten trioxide;
(2) Preparing 13L of 1.0mol/L ferric nitrate solution, under the stirring condition, firstly, gradually adding 1071g of zinc nitrate hexahydrate into the ferric nitrate solution, reacting for 90 minutes, then slowly adding a mixture of nickel nitrate hexahydrate, calcium chloride hexahydrate and tungsten trioxide, reacting for 30 minutes, then slowly adding 714g of zinc nitrate hexahydrate, reacting for 80 minutes, and then adding 55.9g of polyacrylamide serving as a binder to obtain slurry of a precursor precipitate;
(3) Stirring the slurry obtained in the step (2) for 60 minutes, and gradually adding ammonia water with the concentration of 10% into the slurry to adjust the pH value of the slurry to 7.5;
(4) Placing the slurry after the pH is adjusted in the step (3) in an environment of 90 ℃ for thermal modification, wherein the modification time is 120 minutes;
(5) And (3) filtering the modified slurry obtained in the step (4), washing the filtered slurry with tap water and distilled water to enable the pH value of the slurry to reach 7.5, adjusting the solid content to 40%, enabling the slurry to pass through a spray forming tower, controlling the inlet temperature to be 300 ℃ and the outlet temperature to be 100 ℃, and roasting and modifying the slurry at 400 ℃ for 12 hours to obtain the finished catalyst mainly comprising Zn 6 Ni 0.05 Ca 0.1 W 0.1. Fe 13 O 26.
Example 5
This example provides an oxidative dehydrogenation catalyst, the specific preparation process of which comprises the following steps:
(1) firstly, 1200g of chromium sulfate serving as a precursor of metal A, 87.3g of cobalt sulfate heptahydrate serving as a precursor of metal B, 101g of magnesium chloride hexahydrate serving as a precursor of metal C and 2.3g of tungsten trioxide serving as a precursor of metal D are ground into a microspherical shape with a mesh size of 90 meshes; secondly, dividing the chromium sulfate into 660g and 540g according to the proportion of 55 percent and 45 percent, and uniformly mixing cobalt sulfate heptahydrate, magnesium chloride hexahydrate and tungsten trioxide;
(2) Preparing 60L of 0.3mol/L ferric nitrate solution, under the stirring condition, firstly, gradually adding 660g of chromium sulfate into the ferric nitrate solution, reacting for 90 minutes, then, slowly adding a mixture of cobalt sulfate heptahydrate, magnesium chloride hexahydrate and tungsten trioxide, reacting for 60 minutes, then, slowly adding 540g of chromium sulfate, reacting for 60 minutes, and then, adding 8.7g of binder polyvinyl alcohol to obtain slurry of precursor precipitate;
(3) stirring the slurry obtained in the step (2) for 40 minutes, and gradually adding ammonia water with the concentration of 20% into the slurry to adjust the pH value of the slurry to 8.5;
(4) Placing the slurry after the pH is adjusted in the step (3) in an environment of 80 ℃ for thermal modification, wherein the modification time is 70 minutes;
(5) And (3) filtering the modified slurry obtained in the step (4), washing the slurry by using desalted water and deionized water to enable the pH value of the slurry to reach 7.2, adjusting the solid content to be 5%, enabling the slurry to pass through a spray forming tower, controlling the inlet temperature to be 400 ℃ and the outlet temperature to be 125 ℃, and roasting and modifying the slurry at 500 ℃ for 6 hours to obtain the finished product catalyst mainly comprising Cr 3 Co 0.3 Mg 0.5 W 0.01. Fe 18 O 30.8.
example 6
this example provides an oxidative dehydrogenation catalyst, the specific preparation process of which comprises the following steps:
(1) firstly, grinding 1245g of a precursor of metal A, namely copper sulfate pentahydrate, 2.9g of precursor of B, namely cobalt nitrate hexahydrate, 33.6g of precursor of C, and 18.5g of precursor of D, namely tungsten trioxide, into a microspherical shape with a mesh of 100; secondly, dividing copper sulfate pentahydrate into 747g and 498g according to the proportion of 60 percent and 40 percent, and uniformly mixing cobalt nitrate hexahydrate, calcium oxide and tungsten trioxide;
(2) preparing 40L of 0.1mol/L ferric nitrate solution, under the stirring condition, firstly, gradually adding 747g of copper sulfate pentahydrate into the ferric nitrate solution, reacting for 60 minutes, then slowly adding a mixture of cobalt nitrate hexahydrate, calcium oxide and tungsten trioxide, reacting for 90 minutes, then slowly adding 498g of copper sulfate pentahydrate, reacting for 20 minutes, and then adding 55.9g of binder sesbania powder to obtain a slurry of a precursor precipitate;
(3) Stirring the slurry obtained in the step (2) for 60 minutes, and gradually adding ammonia water with the concentration of 15% into the slurry to adjust the pH value of the slurry to 9.0;
(4) placing the slurry after the pH is adjusted in the step (3) in an environment of 95 ℃ for thermal modification, wherein the modification time is 60 minutes;
(5) filtering the modified slurry in the step (4), washing with distilled water and desalted water to make the pH value of the slurry reach 7.0, roasting and modifying the filter cake at 100 ℃ for 6 hours, roasting and modifying at 200 ℃ for 8 hours, roasting and modifying at 300 ℃ for 1 hour, roasting and modifying at 550 ℃ for 1 hour, cooling and grinding, screening out 60-100-mesh catalyst microspheres, and obtaining the finished catalyst mainly comprising Cu 5 Co 0.01 Ca 0.6 W 0.08. Fe 4 O 11.9.
example 7
This example provides an oxidative dehydrogenation catalyst prepared essentially according to the procedure and material ratios of example 1, except that: in step (1) of this example, each metal precursor was not subjected to polishing treatment.
Example 8
this example provides an oxidative dehydrogenation catalyst prepared essentially according to the procedure and material ratios of example 1, except that: in the step (1), the precursor A is not divided into two parts according to the proportion; in the step (2), after the precursor of the metal a is added to the ferric nitrate solution at one time, the reaction is carried out for 160 minutes, and then a mixture of nickel nitrate hexahydrate, calcium chloride hexahydrate and tungsten trioxide is added.
Comparative example 1
This comparative example provides an oxidative dehydrogenation catalyst comparable to the products of examples 1-8, prepared essentially according to the preparation and charge ratios of example 1, except that: no metal D (tungsten) was used in the catalyst preparation.
Example 9
This example provides a mixed C4 conversion utilization process, where the materials and catalysts used in the process are as follows:
The olefin oxidative dehydrogenation catalyst is prepared by adopting the olefin oxidative dehydrogenation catalyst prepared in example 1, and mainly comprises Zn 6 Ni 0.3 Ca 0.9 W 0.02 & Fe 17 O 32.7. the etherification catalyst adopts a KC-116 type resin catalyst produced by Kelly chemical company, the particle size range of the etherification catalyst is more than or equal to 99 percent (0.355-1.250mm), the wet true density is 1150-1250g/l, the total exchange capacity is more than or equal to 1.7mmol/ml [ H + ], the mechanical strength is more than or equal to 98 percent (H type). Theai HTPB-DH dehydrogenation catalyst is adopted, wherein Al 2 O 3 is used as a carrier, Pt and Cl are used as active components, the mass content of Pt is 1 percent, the mass content of chlorine is 2 percent, the specific surface area is 200m 2/g, the pore volume is 0.5ml/g, the diameter is 1.59mm, and the bulk density is 0.6g/cm 3.
The mixed C4 raw material is used as a raw material A (the specific composition is shown in Table 1).
The process provided by the embodiment at least comprises the following steps:
The first step, preheating a mixed C4 raw material, air and water, and then sending the mixture into an oxidative dehydrogenation reactor (R1) for alkane oxidative dehydrogenation, wherein the oxidative dehydrogenation reaction conditions comprise that the temperature is 340 ℃, the pressure is atmospheric pressure, the volume space velocity is 400h -1, the molar ratio of olefin to oxygen in all hydrocarbon materials entering the oxidative dehydrogenation reactor is 1:0.68, the mass ratio of all hydrocarbon materials entering the oxidative dehydrogenation unit to water is 1:12, the mass yield of dialkene is 61.3%, the mass yield of alcohol is 0.81%, and the mass yield of ketone is 0.55%;
The reaction product of the oxidative dehydrogenation is fed to a separation unit I (T1) for separation into butadiene, a carbon four fraction other than butadiene and the remaining components;
secondly, feeding the four carbon fractions obtained in the first step except butadiene and methanol into an etherification reactor (R2) for etherification reaction, wherein the etherification reaction conditions comprise the reaction temperature of 45 ℃, the volume space velocity of 2h -1, the reaction pressure of 1.5MPa, the molar ratio of the methanol to isobutene in hydrocarbon materials entering the etherification reactor of 1.2:1, and the mass yield of ether compounds in etherification reaction products is 42.7%;
feeding the etherification product into a separation unit II (T2) to separate the etherification product into five-carbon and above components, four-carbon hydrocarbon and the rest components (mainly containing ether compounds);
Thirdly, the hydrocarbon with four carbon atoms and hydrogen obtained in the second step are sent into a catalytic dehydrogenation reactor (R3) for alkane catalytic dehydrogenation reaction, wherein the reaction conditions are that the reaction temperature is 480 ℃, the volume space velocity is 0.1h -1, the reaction pressure is 0.01MPa, the molar ratio of the hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit is 0.25:1, and the olefin content in the catalytic dehydrogenation product after the reaction is 37.4 percent;
The reaction product is sent to a separation unit III (T3) to be separated into a non-condensable gas and the remaining components (mainly carbon tetrahydrocarbons), and the remaining components are returned to the oxidative dehydrogenation unit in the first step.
Example 10
This example provides a mixed C4 conversion utilization process, where the materials and catalysts used in the process are as follows:
The olefin oxidative dehydrogenation catalyst is prepared by adopting the catalyst prepared in the embodiment 2 and mainly comprises Cu 2.5 Co 0.4 Ba 0.1 W 0.06. Fe 18 O 30.2. the etherification catalyst adopts D005-II resin catalyst produced by Dandong Mingzhu special resin Co., Ltd. the particle size range is 0.315-1.25mm, the wet true density is 1180-1200g/l, the total exchange capacity is not less than 5.2mmol/g [ H + ], the mechanical strength is not less than 95% (H type). the catalytic dehydrogenation catalyst is prepared by adopting the method of the embodiment 4 in CN 101940922A. the specific steps are that 117.5 g of chromic oxide is weighed and dissolved in deionized water to be fully stirred to prepare a chromic oxide solution with the weight concentration of 47%, then potassium nitrate aqueous solution with the weight concentration of 3.86% is prepared, 55.0 g of pseudo-boehmite, 2.2 g of bentonite and 7.59 g of prepared chromic oxide solution are fully mixed, kneaded, extruded into small balls, then dried at the constant temperature of 120 ℃ for 3 hours, dried for standby at the constant temperature of 3 hours, finally dried at the constant temperature of 120 ℃ for 3 hours, dried at the constant temperature of 120 ℃ of 120.0 ℃ for 3 hours, dried at the constant temperature of 120 ℃ for 3 hours, dried at the constant temperature of 120.2 hours, dried at the constant temperature of 550 ℃ of 120 ℃, dried at the constant temperature of 120 ℃ of 3 hours, dried at the constant temperature of 0g of the constant temperature.
The mixed C4 raw material is used as a raw material B (the specific composition is shown in Table 2).
The process provided by the embodiment at least comprises the following steps:
The first step is that the mixed C-C raw material, oxygen-enriched airflow containing 45 percent of oxygen and water are preheated and then sent into an oxidative dehydrogenation reactor (R1) for alkane oxidative dehydrogenation reaction, wherein the oxidative dehydrogenation reaction conditions are that the temperature is 350 ℃, the pressure is 100KPa, the volume space velocity is 10h -1, the mole ratio of olefin to oxygen in all hydrocarbon materials entering the oxidative dehydrogenation reactor is 1:0.3, the mass ratio of all hydrocarbon materials entering the oxidative dehydrogenation unit to water is 1:30, the mass yield of diene in reaction products is 52.4 percent, the mass yield of alcohol is 0.51 percent, and the mass yield of ketone is 0.27 percent;
the reaction product of the oxidative dehydrogenation is fed to a separation unit I (T1) for separation into butadiene, a carbon four fraction other than butadiene and the remaining components;
Secondly, feeding the four carbon fractions obtained in the first step except butadiene and methanol into an etherification reactor (R2) for etherification reaction, wherein the etherification reaction conditions comprise the reaction temperature of 80 ℃, the volume space velocity of 3.0h -1, the reaction pressure of 1.0MPa, the molar ratio of the methanol to isobutene in hydrocarbon materials entering the etherification reactor of 1.1:1, and the mass yield of ether compounds in etherification reaction products is 40.6%;
Feeding the etherification product into a separation unit II (T2) to separate the etherification product into five-carbon and above components, four-carbon hydrocarbon and the rest components (mainly containing ether compounds);
Thirdly, the hydrocarbon with four carbon atoms and hydrogen obtained in the second step are sent into a catalytic dehydrogenation reactor (R3) for alkane catalytic dehydrogenation reaction, wherein the reaction conditions are that the reaction temperature is 700 ℃, the volume space velocity is 1.0h -1, the reaction pressure is 0.15Mpa, the molar ratio of the hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit is 0.1:1, and the olefin content in the catalytic dehydrogenation product after the reaction is 51.8 percent;
the reaction product is sent to a separation unit III (T3) to be separated into a non-condensable gas and a residual component (mainly containing carbon tetrahydrocarbon), and the residual component is returned to the oxidative dehydrogenation unit in the first step.
example 11
This example provides a mixed C4 conversion utilization process, where the materials and catalysts used in the process are as follows:
The olefin oxidative dehydrogenation catalyst is prepared by adopting the olefin oxidative dehydrogenation catalyst prepared in the preparation example 3, and mainly comprises Zn 1 Mn 0.15 Sr 1 W 0.06. Fe 7 O 12.8. the etherification catalyst adopts NKC-9 cation exchange resin catalyst produced by chemical plants of southern Kao university, the particle size range of the etherification catalyst is more than or equal to 95 percent (0.4-1.25mm), the specific surface area is 77m 2/g, the pore volume is 0.27ml/g, the total exchange volume is more than or equal to 4.7mmol/g [ H + ], the dehydrogenation catalyst is prepared by adopting the method of the example 1 in the patent CN101618319, 2.24 g of calcium oxide and 3.1g of polyethylene glycol are dissolved in 120ml of deionized water, the mixture is subjected to hydrothermal treatment at 240 ℃ for 24 hours, the mixture is burnt at 600 ℃ for 5 hours, and then is uniformly mixed with a proper amount of anhydrous ethanol, 7.2 g of chromium nitrate and 6g of aluminum oxide, is uniformly ground after being dried for twelve hours, and is burnt at 550 ℃ for standby after.
the process provided by the embodiment at least comprises the following steps:
the method comprises the following steps of firstly, preheating a mixed C-C raw material A (the composition is shown in table 1), oxygen-enriched airflow containing 35% of oxygen and water, and then feeding the preheated raw material A, the oxygen-enriched airflow and the water into an oxidative dehydrogenation reactor (R1) to perform alkane oxidative dehydrogenation, wherein the oxidative dehydrogenation reaction conditions comprise that the temperature is 380 ℃, the pressure is 50KPa, the volume space velocity is 60h -1, the molar ratio of olefin to oxygen in all hydrocarbon materials entering the oxidative dehydrogenation reactor is 1:0.1, the mass ratio of all hydrocarbon materials entering the oxidative dehydrogenation unit to water is 1:5, the mass yield of diene in reaction products is 59.3%, the mass yield of alcohol is 0.43%, and the mass yield of ketone is 0.20%;
the reaction product of the oxidative dehydrogenation is fed to a separation unit I (T1) for separation into butadiene, a carbon four fraction other than butadiene and the remaining components;
Secondly, feeding the four carbon fractions obtained in the first step except butadiene and methanol into an etherification reactor (R2) for etherification reaction, wherein the etherification reaction conditions comprise the reaction temperature of 65 ℃, the volume space velocity of 4h -1, the reaction pressure of 0.5MPa, the molar ratio of the methanol to isobutene in hydrocarbon materials entering the etherification reactor of 1.3:1, and the mass yield of ether compounds in etherification reaction products is 55.7%;
Feeding the etherification product into a separation unit II (T2) to separate the etherification product into five-carbon and above components, four-carbon hydrocarbon and the rest components (mainly containing ether compounds);
Thirdly, the hydrocarbon with four carbon atoms and hydrogen obtained in the second step are sent into a catalytic dehydrogenation reactor (R3) for alkane catalytic dehydrogenation reaction, wherein the reaction conditions are that the reaction temperature is 570 ℃, the volume space velocity is 3.0h -1, the reaction pressure is 1.7MPa, the molar ratio of the hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit is 0.01:1, and the olefin content in the catalytic dehydrogenation product after the reaction is 55.3 percent;
The reaction product is sent to a separation unit III (T3) to be separated into a non-condensable gas and the remaining components (mainly carbon tetrahydrocarbons), and the remaining components are returned to the oxidative dehydrogenation unit in the first step.
example 12
This example provides a mixed C4 conversion utilization process, where the materials and catalysts used in the process are as follows:
Olefin oxidative dehydrogenation catalyst the catalyst prepared in example 4 was prepared using an olefin oxidative dehydrogenation catalyst consisting essentially of Zn 6 Ni 0.05 Ca 0.1 W 0.1 · Fe 13 O 26, the etherification catalyst used was a macroporous strong acid resin catalyst produced by the company tasselo petrochemical technology limited having a particle size of 0.315 to 1.25mm, a bulk density of 0.77 to 0.85g/ml, a specific surface area of greater than 20 to 70m 2/g, a pore diameter of greater than 20 to 50nm, a pore volume of greater than 0.3 to 0.5cc/g, the dehydrogenation catalyst prepared using the method of example 4 in CN101940922A, and specifically comprising the steps of weighing 117.5 g of chromium oxide, dissolving in deionized water and stirring thoroughly to prepare a chromium oxide solution having a weight concentration of 47%, preparing an aqueous solution having a weight concentration of 3.86%, then preparing 55.0 g of pseudo-thin aluminum potassium nitrate, 2.2 g of bentonite, mixing well with 7.59 g of chromium oxide solution, kneading, drying at constant temperature to prepare a pellet, drying at 120 ℃ for 120.2 hours, drying at constant temperature for 3 hours, drying at 3 ℃ for 3 hours, drying at 550 ℃ for 3 hours, drying at constant temperature for 3 hours, and finally preparing a solution at 550 ℃ for 3 hours, drying at 3 hours, and finally preparing a solution at a temperature of 550 ℃ for 3 hours, drying at 550 ℃ for 3 hours, and a similar to prepare a.
the mixed C4 raw material is used as a raw material B (the specific composition is shown in Table 2).
the process provided by the embodiment at least comprises the following steps:
the first step is that the mixed C-C raw material, oxygen-enriched airflow containing 40% of oxygen and water are preheated and then sent into an oxidative dehydrogenation reactor (R1) for alkane oxidative dehydrogenation reaction, wherein the oxidative dehydrogenation reaction conditions are that the temperature is 390 ℃, the pressure is 20KPa, the volume space velocity is 500h -1, the mole ratio of olefin and oxygen in all hydrocarbon materials entering the oxidative dehydrogenation reactor is 1:0.8, the mass ratio of all hydrocarbon materials entering the oxidative dehydrogenation unit to water is 1:16, the mass yield of diene in reaction products is 53.4%, the mass yield of alcohol is 0.63%, and the mass yield of ketone is 0.31%;
The reaction product of the oxidative dehydrogenation is fed to a separation unit I (T1) for separation into butadiene, a carbon four fraction other than butadiene and the remaining components;
Secondly, feeding the four carbon fractions obtained in the first step except butadiene and methanol into an etherification reactor (R2) for etherification reaction, wherein the etherification reaction conditions comprise the reaction temperature of 75 ℃, the volume space velocity of 5h -1, the reaction pressure of 1.2MPa, the molar ratio of the methanol to isobutene in hydrocarbon materials entering the etherification reactor of 1.5:1, and the mass yield of ether compounds in etherification reaction products is 45.2%;
Feeding the etherification product into a separation unit II (T2) to separate the etherification product into five-carbon and above components, four-carbon hydrocarbon and the rest components (mainly containing ether compounds);
Thirdly, the hydrocarbon with four carbon atoms and hydrogen obtained in the second step are sent into a catalytic dehydrogenation reactor (R3) for alkane catalytic dehydrogenation reaction, wherein the reaction conditions are that the reaction temperature is 600 ℃, the volume space velocity is 5.0h -1, the reaction pressure is 1.1Mpa, the molar ratio of the hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit is 0.3:1, and the olefin content in the catalytic dehydrogenation product after the reaction is 63.6 percent;
the reaction product is sent to a separation unit III (T3) to be separated into a non-condensable gas and the remaining components (mainly carbon tetrahydrocarbons), and the remaining components are returned to the oxidative dehydrogenation unit in the first step.
example 13
this example provides a mixed C4 conversion utilization process, where the materials and catalysts used in the process are as follows:
The olefin oxidative dehydrogenation catalyst is prepared by using the catalyst prepared in example 5, and mainly comprises Cr 3 Co 0.3 Mg 0.5 W 0.01. Fe 18 O 30.8. the etherification catalyst is an etherification resin catalyst produced by Kary chemical Co., Ltd. and has a particle size range of 0.335-1.25mm, a wet true density of 0.75-0.85g/ml, a total exchange capacity of not less than 5.2mmol/g and a mechanical strength of not less than 95%.
The mixed C4 raw material is used as a raw material A (the specific composition is shown in Table 1).
The process provided by the embodiment at least comprises the following steps:
The first step is that the mixed C-C raw material, oxygen-enriched airflow containing 32 percent of oxygen and water are preheated and then sent into an oxidative dehydrogenation reactor (R1) for alkane oxidative dehydrogenation reaction, wherein the oxidative dehydrogenation reaction conditions are that the temperature is 280 ℃, the pressure is 10KPa, the volume space velocity is 300h -1, the mole ratio of olefin and oxygen in all hydrocarbon materials entering the oxidative dehydrogenation reactor is 1:0.55, the mass ratio of all hydrocarbon materials entering the oxidative dehydrogenation unit to water is 1:10, the mass yield of diene in reaction products is 57.8 percent, the mass yield of alcohol is 0.47 percent, and the mass yield of ketone is 0.30 percent;
The reaction product of the oxidative dehydrogenation is fed to a separation unit I (T1) for separation into butadiene, a carbon four fraction other than butadiene and the remaining components;
Secondly, sending the four carbon fractions obtained in the first step except butadiene and ethanol flow into an etherification reactor (R2) for etherification reaction, wherein the etherification reaction conditions comprise reaction temperature of 55 ℃, volume space velocity of 0.1h -1, reaction pressure of 2.0MPa, molar ratio of ethanol to isobutene in hydrocarbon materials entering the etherification reactor of 1.2:1, and mass yield of ether compounds in etherification reaction products of 45.1%;
Feeding the etherification product into a separation unit II (T2) to separate the etherification product into five-carbon and above components, four-carbon hydrocarbon and the rest components (mainly containing ether compounds);
Thirdly, the hydrocarbon and hydrogen obtained in the second step are sent into a catalytic dehydrogenation reactor (R3) to carry out alkane catalytic dehydrogenation reaction, wherein the reaction conditions are that the reaction temperature is 650 ℃, the volume space velocity is 8.0h -1, the reaction pressure is 2.4Mpa, the molar ratio of the hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit is 0.15:1, and the olefin content in the catalytic dehydrogenation product after the reaction is 35.3 percent;
The reaction product was sent to a separation unit III (T3) to be separated into a non-condensable gas and the remaining components ((mainly carbon tetrahydrocarbons)), which were returned to the oxidative dehydrogenation unit of the first step.
Example 14
This example provides a mixed C4 conversion utilization process, where the materials and catalysts used in the process are as follows:
olefin oxidative dehydrogenation catalyst the catalyst prepared in example 6 was prepared using an olefin oxidative dehydrogenation catalyst consisting essentially of Cu 5 Co 0.01 Ca 0.6 W 0.08. Fe 4 O 11.9 zeolite etherification catalyst developed by the institute of petrochemical sciences, which was spherical in shape with a diameter of 8mm in external form, a bulk density of 0.71g/cm 3, a specific surface area of 487M 2/g, a pore volume of 0.464mL/g, an average pore diameter of 175nm, and a strength of >20 n. the dehydrogenation catalyst was prepared using the procedure of the catalyst preparation in example 1 of patent CN101623633A, ZSM-5 molecular sieve raw powder was first immersed in a 0.16M SnCl 2.2H 2 O solution at 80 ℃ for 10hr to achieve a Sn loading of 4 wt% in the catalyst, then the dried sample at 120 ℃ for 6hr after drying at 550 ℃ for 4hr, the powder after drying at 550 ℃ for 4hr, the loading of Pt 3 cl 6.6H 2 hr after calcination at 550 ℃ for a standby hydrogen at 550 ℃ for reduction at 550 ℃ to obtain a final catalyst having a Pt loading of Pt 4 wt% in Pt 3 cl 73742H 84, and after calcination at 550 ℃ for reduction at 550 ℃ for a final reduction at 20 ℃ for a final reduction.
The process provided by the embodiment at least comprises the following steps:
The method comprises the following steps of firstly, preheating a mixed C-C raw material A (the composition is shown in table 1), oxygen-enriched airflow containing 32% of oxygen and water, and then feeding the preheated mixed C-C raw material A, the oxygen-enriched airflow containing 32% of oxygen and the water into an oxidative dehydrogenation reactor (R1) to perform alkane oxidative dehydrogenation, wherein the oxidative dehydrogenation reaction conditions comprise that the temperature is 340 ℃, the pressure is 70KPa, the volume space velocity is 250h -1, the molar ratio of olefin to oxygen in all hydrocarbon materials entering the oxidative dehydrogenation reactor is 1:0.1, the mass ratio of all hydrocarbon materials entering the oxidative dehydrogenation unit to water is 1:0.5, the mass yield of diene in reaction products is 47.0%, the mass yield of alcohol is 1.01%, and the mass yield of ketone is 0.79%;
the reaction product of the oxidative dehydrogenation is fed to a separation unit I (T1) for separation into butadiene, a carbon four fraction other than butadiene and the remaining components;
secondly, sending the other carbon four fractions except butadiene obtained in the first step and alcohol material flow into an etherification reactor (R2) for etherification reaction, wherein the etherification reaction conditions comprise reaction temperature of 30 ℃, volume space velocity of 0.5h -1, reaction pressure of 1.7MPa, molar ratio of methanol to isobutene in hydrocarbon materials entering the etherification reactor of 0.95:1, and mass yield of ether compounds in etherification reaction products of 35.6%;
Feeding the etherification product into a separation unit II (T2) to separate the etherification product into five-carbon and above components, four-carbon hydrocarbon and the rest components (mainly containing ether compounds);
Thirdly, the hydrocarbon with four carbon atoms and hydrogen obtained in the second step are sent into a catalytic dehydrogenation reactor (R3) for alkane catalytic dehydrogenation reaction, wherein the reaction conditions are that the reaction temperature is 550 ℃, the volume space velocity is 10.0h -1, the reaction pressure is 3.0Mpa, the molar ratio of the hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit is 0.5:1, and the olefin content in the catalytic dehydrogenation product after the reaction is 44.3 percent;
the reaction product is sent to a separation unit III (T3) to be separated into a non-condensable gas and the remaining components (mainly carbon tetrahydrocarbons), and the remaining components are returned to the oxidative dehydrogenation unit in the first step.
Example 15
this example provides a mixed carbon four conversion utilization process, which is substantially the same as example 9, except that: the oxidative dehydrogenation catalyst used was the oxidative dehydrogenation catalyst prepared in example 7.
Parameters of part of the product in the process:
In the first step, the mass yield of the diolefin is 40.2%, the mass yield of the alcohols is 0.81%, and the mass yield of the ketones is 0.43%;
In the second step, the mass yield of ether compounds in the etherification reaction products is 63.5 percent;
In the third step, the olefin content in the catalytic dehydrogenation product after the reaction was 37.6%.
Example 16
This example provides a mixed carbon four conversion utilization process, which is substantially the same as example 9, except that: the oxidative dehydrogenation catalyst used was the oxidative dehydrogenation catalyst prepared in example 8.
parameters of part of the product in the process:
In the first step, the mass yield of diolefins is 38.4%, the mass yield of alcohols is 0.81%, and the mass yield of ketones is 0.43%;
In the second step, the mass yield of ether compounds in the etherification reaction products is 65.3 percent;
In the third step, the olefin content in the catalytic dehydrogenation product after the reaction was 37.6%.
comparative example 2
This comparative example provides a prior art mixed carbon four conversion process, as compared to examples 9-16, as follows:
Etherification catalyst RZE-3 zeolite etherification catalyst was purchased from petrochemical academy of sciences, the external form was spherical with a diameter of 8mm, the bulk density was 0.71g/cm 3, the specific surface area was 487M 2/g, the pore volume was 0.464mL/g, the average pore diameter was 175nm, and the strength was >20 n. dehydrogenation catalyst was prepared using the procedure of catalyst preparation in example 1 of patent CN 101623633A. ZSM-5 molecular sieve raw powder was first immersed in 0.16M SnCl 2.2H 2 O solution at 80 ℃ for 10hr so that the loading of Sn in the catalyst reached 4 wt%, then dried at 120 ℃ for 6hr, the calcined sample was calcined at 550 ℃ for 4hr, and the calcined powder was impregnated at 80 ℃ for 4hr in 0.03M H 2 PtCl 6.6H 2 O solution to finally prepare a catalyst with a Pt content of 20 wt%, then dried at 120 ℃ for 6hr, calcined at 550 ℃ for 4hr, and then reduced with hydrogen at 550 ℃ for 12 hr.
The mixed C-IV raw material is a raw material B (the components are shown in Table 2), the raw material B and methanol are mixed and enter an etherification reactor, the etherification reaction conditions are that the reaction temperature is 73 ℃, the volume space velocity is 1.4h -1, and the reaction pressure is 1.7MPa, wherein the molar ratio of the methanol to the isobutane in the hydrocarbon material entering the etherification reactor is 0.95:1, ether compounds are separated through a separation unit, the yield is 34.1%, the molar ratio of hydrogen to all hydrocarbon materials entering a catalytic deoxidation unit in a dehydrogenation reactor is 0.5:1, the reaction is carried out under the conditions that the reaction temperature is 550 ℃, the volume space velocity is 10.0h -1, and the reaction pressure is 3.0MPa, and the olefin content in the dehydrogenation product is 42.5%.
comparative example 3
This example provides a mixed carbon four conversion utilization process comparable to examples 9-16, substantially using the process of example 9, except that: the oxidative dehydrogenation catalyst used was the catalyst prepared in comparative example 1.
Parameters of part of the product in the process:
In the first step, the mass yield of the diolefin is 24.1%, the mass yield of the alcohols is 0.74%, and the mass yield of the ketones is 0.50%;
in the second step, the mass yield of the ether compound in the etherification reaction product is 36.1 percent;
In the third step, the olefin content in the catalytic dehydrogenation product after the reaction was 37.5%.
Claims (34)
1. the process for converting and utilizing mixed C4 is characterized by at least comprising the following steps:
The first step is as follows: sending the mixed C-C raw material, a material flow containing an oxidant and water or steam into an oxidative dehydrogenation unit for alkane oxidative dehydrogenation reaction, and sending a reaction product into a separation unit I for separation into butadiene, other C-C fractions except the butadiene and the rest components;
The second step is that: feeding the other carbon four fractions except butadiene obtained in the first step and alcohol material flow into an etherification reaction unit for etherification reaction, and feeding reaction products into a separation unit II for separation into components with five or more carbon atoms, hydrocarbon with four carbon atoms and the rest components;
the third step: feeding the carbon tetrahydrocarbon and hydrogen obtained in the second step into a catalytic dehydrogenation unit for alkane catalytic dehydrogenation reaction, feeding a reaction product into a separation unit III for separation into noncondensable gas and residual components, and returning the residual components to the oxidative dehydrogenation unit in the first step;
In the first step, the oxidative dehydrogenation catalyst used in the oxidative dehydrogenation unit is represented by formula (I):
a a B b C c D d. Fe x O e formula (I)
In formula (I): a is Cu, Zn or Cr; b is Co, Mn, Ni or Mo; c is Ca, Sr, Ba or Mg; d is W; a is 1 to 6, b is 0.01 to 0.3, c is 0.1 to 1.0, d is 0.01 to 0.1, x is 4 to 18, and e is any value meeting the valence requirement;
The content of the carbon tetraolefin in the mixed carbon four raw material is not lower than 40%.
2. The conversion utilization process according to claim 1, characterized in that in formula (I): a is 3-5, b is 0.05-0.15, c is 0.3-0.6, d is 0.04-0.08, and x is 7-13.
3. The conversion utilization process according to claim 1, wherein the sum of the mass contents of n-butene and n-butane in the mixed C4 feedstock is not less than 35%.
4. The conversion utilization process according to claim 3, wherein the sum of the mass contents of n-butene and n-butane in the mixed C4 feedstock is not less than 40%.
5. The conversion utilization process of claim 1, wherein the oxidative dehydrogenation unit has reaction conditions of 280-410 deg.C, 0-100KPa pressure, and 10-500 hr -1 volume space velocity.
6. The conversion utilization process of claim 5, wherein the oxidative dehydrogenation unit has reaction conditions of 310-390 ℃, 0-40KPa of pressure and 60-400h -1 of volume space velocity.
7. the conversion utilization process of claim 1, wherein the oxidant-containing stream is a stream containing molecular oxygen or strongly oxidizing oxygen atoms.
8. The conversion utilization process of claim 7, wherein the oxidant-containing stream is air, oxygen-enriched gas, or oxygen.
9. the conversion utilization process of claim 8, wherein the molar ratio of the oxidant to the olefin in all hydrocarbon feed entering the oxidative dehydrogenation unit is 0.1 to 1.0:1, calculated as oxygen, upon entering the oxidative dehydrogenation unit.
10. the conversion utilization process of claim 9, wherein the molar ratio of the oxidant to the olefin in all hydrocarbon feed entering the oxidative dehydrogenation unit, calculated as oxygen, is from 0.3 to 0.85: 1.
11. The conversion utilization process of claim 1, wherein the mass ratio of water or steam to butenes in the total hydrocarbon feed to the oxidative dehydrogenation unit is from 0.5 to 30 when entering the oxidative dehydrogenation unit.
12. The conversion utilization process of claim 11, wherein the mass ratio of water or steam to butenes in the total hydrocarbon feed to the oxidative dehydrogenation unit is 5 to 20 when entering the oxidative dehydrogenation unit.
13. the conversion utilization process according to claim 1, wherein the mass content of butadiene in the carbon four-cut fraction other than butadiene is not higher than 0.3%.
14. The conversion utilization process according to claim 13, wherein the mass content of butadiene in the carbon four-cut fraction other than butadiene is not higher than 0.1%.
15. The conversion utilization process according to claim 1, wherein the molar ratio of the alcohol to isobutylene in all hydrocarbon materials entering the etherification reaction unit is 0.8-1.5: 1.
16. the conversion utilization process of claim 15, wherein the molar ratio of the alcohol to isobutylene in all hydrocarbon feed entering the etherification unit is 1.1 to 1.3: 1.
17. the conversion utilization process of claim 1, wherein the reaction conditions of the etherification reaction unit are that the temperature is 30-100 ℃, the pressure is 0.1-2.0MPa, and the volume space velocity is 0.1-5h -1.
18. The conversion utilization process of claim 17, wherein the reaction conditions of the etherification reaction unit are 45-80 ℃, the pressure of 0.5-1.5MPa and the volume space velocity of 1-2h -1.
19. The conversion utilization process according to claim 1, wherein the conversion of isobutylene in the etherification reaction unit is not less than 92%.
20. The conversion utilization process according to claim 1, wherein the mass content of the carbon four component in the carbon four hydrocarbon separated by the separation unit II is not less than 97%.
21. The conversion utilization process according to claim 20, wherein the mass content of the carbon four component in the carbon four hydrocarbon separated by the separation unit II is not less than 99%.
22. The conversion utilization process according to claim 1, wherein the reaction product of the catalytic dehydrogenation unit has an olefin content of not less than 35% by mass.
23. The conversion utilization process of claim 22, wherein the mass content of olefins in the reaction product of the catalytic dehydrogenation unit is greater than 45%.
24. the conversion and utilization process as claimed in claim 1, wherein the reaction conditions of the catalytic dehydrogenation unit are 480 ℃ and 700 ℃, the pressure is 0.01-3MPa, and the liquid hourly space velocity is 0.1-10h -1.
25. The conversion utilization process as claimed in claim 24, wherein the reaction conditions of the catalytic dehydrogenation unit are 560 ℃ and 650 ℃, the pressure is 0.4-1.2MPa, and the liquid hourly space velocity is 2-7h -1.
26. The conversion utilization process of claim 25, wherein the molar ratio of hydrogen to all hydrocarbon feed entering the catalytic dehydrogenation unit is from 0.01 to 1:1 upon entering the catalytic dehydrogenation unit.
27. the conversion utilization process of claim 26, wherein the molar ratio of hydrogen to all hydrocarbon feed entering the catalytic dehydrogenation unit is from 0.1 to 0.5:1 upon entering the catalytic dehydrogenation unit.
28. The conversion utilization process of claim 1, wherein two or more fixed bed catalytic dehydrogenation reactors are used in parallel in the catalytic dehydrogenation unit.
29. The conversion utilization process according to any one of claims 1 to 28, wherein the oxidative dehydrogenation catalyst is prepared by a process comprising the steps of:
(1) Respectively grinding precursors of the used metals A, B, C and D into microspheres with 40-100 meshes; dividing the grinded precursor of the metal A into two parts by weight; simultaneously, uniformly mixing precursors of the metal B, C and the D;
(2) Preparing 0.1-2mol/L ferric nitrate solution, gradually adding a first part of precursor of metal A into the ferric nitrate solution under the condition of stirring, reacting for 30-90 minutes, adding the precursor of metal B, C and D which are uniformly mixed, continuing to react for 30-90 minutes, adding a second part of precursor of metal A, continuing to react for 20-80 minutes, and adding a binder to obtain slurry of precursor precipitate;
(3) stirring the slurry obtained in the step (2) for 20-60 minutes, and gradually adding ammonia water with the concentration of 10-25% into the slurry to adjust the pH value of the slurry to 7.5-10.0;
(4) placing the slurry after the pH is adjusted in the step (3) in an environment of 80-95 ℃ for thermal modification, wherein the modification time is 60-180 minutes;
(5) filtering the modified slurry obtained in the step (4), washing with washing water to enable the pH value of the slurry to reach 7-7.5, adjusting the solid content of the slurry to be 5-40%, then performing spray forming, and roasting at 400-500 ℃ for 6-12 hours to obtain a finished catalyst;
Or filtering the modified slurry in the step (4), washing with washing water, and enabling the pH value of the slurry to reach 7-7.5, then roasting at 100-200 ℃ for 6-12 hours, at 200-300 ℃ for 4-8 hours, at 300-400 ℃ for 1-4 hours, at 400-500 ℃ for 1-4 hours, and grinding to obtain the finished catalyst.
30. the conversion utilization process of claim 29, wherein in step (1) of the preparation of the oxidative dehydrogenation catalyst, the first portion of the metal a precursor is 55 to 70% of the total weight of the metal a precursor.
31. The conversion utilization process of claim 29, wherein in step (1) of the preparation of the oxidative dehydrogenation catalyst, the precursors of metals A, B, C and D are each selected from the group consisting of one or more of nitrates, chlorides, sulfates, and oxides of the respective metals.
32. the conversion utilization process of claim 29, wherein in step (2) of the preparation of the oxidative dehydrogenation catalyst, the binder comprises one or a combination of sesbania powder, polyacrylamide, methylcellulose, and polyvinyl alcohol.
33. the conversion use process according to claim 32, wherein the binder is added in an amount of 0.1 to 4% by mass based on the total mass of the metal precursor.
34. The conversion utilization process according to claim 29, wherein in the step (5) of the preparation process of the oxidative dehydrogenation catalyst, the feed temperature of the spray tower is 300-500 ℃ and the discharge temperature is 100-150 ℃ in the spray formation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101119949A (en) * | 2005-01-17 | 2008-02-06 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
| CN101555197A (en) * | 2008-04-11 | 2009-10-14 | 中国石油化工股份有限公司 | Comprehensive use method of mixed C-4 |
| CN103831114A (en) * | 2012-11-21 | 2014-06-04 | 上海华谊丙烯酸有限公司 | Ferrite catalyst, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166454A (en) * | 1990-03-19 | 1992-11-24 | Mobil Oil Corporation | Etherification process with hydrogen rejuvenation |
| US9399606B2 (en) * | 2012-12-06 | 2016-07-26 | Basf Se | Catalyst and process for the oxidative dehydrogenation of N-butenes to butadiene |
-
2015
- 2015-12-14 CN CN201510923693.6A patent/CN106866337B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101119949A (en) * | 2005-01-17 | 2008-02-06 | 巴斯福股份公司 | Method for producing butadiene from n-butane |
| CN101555197A (en) * | 2008-04-11 | 2009-10-14 | 中国石油化工股份有限公司 | Comprehensive use method of mixed C-4 |
| CN103831114A (en) * | 2012-11-21 | 2014-06-04 | 上海华谊丙烯酸有限公司 | Ferrite catalyst, preparation method and application thereof |
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