CN112225654A - Device and method for comprehensively utilizing mixed C4 - Google Patents
Device and method for comprehensively utilizing mixed C4 Download PDFInfo
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- CN112225654A CN112225654A CN202011205725.6A CN202011205725A CN112225654A CN 112225654 A CN112225654 A CN 112225654A CN 202011205725 A CN202011205725 A CN 202011205725A CN 112225654 A CN112225654 A CN 112225654A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- 238000000926 separation method Methods 0.000 claims abstract description 89
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 34
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000005336 cracking Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 31
- 150000001299 aldehydes Chemical class 0.000 claims description 29
- 239000007795 chemical reaction product Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 19
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 8
- 239000000306 component Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 239000001273 butane Substances 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 7
- 238000006170 formylation reaction Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000011552 falling film Substances 0.000 claims description 3
- LNQFKNCJGVGEGA-UHFFFAOYSA-N [Rh+6].[O-]P([O-])[O-].[O-]P([O-])[O-] Chemical compound [Rh+6].[O-]P([O-])[O-].[O-]P([O-])[O-] LNQFKNCJGVGEGA-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005977 Ethylene Substances 0.000 abstract description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005899 aromatization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- NKQYVXQKXPHGCV-UHFFFAOYSA-N [Rh+4].[O-]P([O-])OP([O-])[O-] Chemical compound [Rh+4].[O-]P([O-])OP([O-])[O-] NKQYVXQKXPHGCV-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a device and a method for comprehensively utilizing mixed C4, wherein the device comprises a hydroformylation unit, a catalyst separation unit and a light component separation unit which are sequentially connected; the catalyst solution outlet of the catalyst separation unit is connected with the liquid inlet of the catalyst treatment unit; the liquid outlet of the catalyst treatment unit is connected with the catalyst inlet of the hydroformylation unit; and a light component outlet of the light component separation unit is connected with a cracking unit. The device provided by the invention avoids the separation of butene products through hydroformylation reaction, and simultaneously cracks unreacted components, so that the yield of ethylene and propylene is increased, and the value of carbon four products is fully utilized.
Description
Technical Field
The invention relates to the field of comprehensive utilization, in particular to a device and a method for comprehensively utilizing mixed carbon four.
Background
At present, the mixed carbon four is mainly derived from refinery carbon four, cracking carbon four and a byproduct carbon four in a methanol to olefin (MTO, MTP and CMTX) process, and the components of the mixed carbon four have large differences due to different sources. Because the boiling points of all components in the mixed C4 are relatively close, the complete separation by rectification is very difficult, and the current main utilization modes are as follows: aromatization of carbon four, preparation of gasoline by carbon four alkylation, preparation of ethylene and propylene by direct cracking of carbon four, production of MTBE, production of butene-1 and polybutene, etc. Under the influence of consumption tax and new government, the industrial chain of mixed aromatics obtained by aromatization of liquefied gas as blended gasoline may decline, the industry of aromatization of liquefied gas is slow, the application of direct alkylation technology is limited due to the pollution problem of catalyst, the product market of MTBE is severely limited along with the popularization of ethanol gasoline, isobutene and butene-1 are difficult to separate without an MTBE device.
For example, CN101555197A discloses a method for comprehensively utilizing mixed carbon four, which mainly solves the problem of low comprehensive utilization rate of the mixed carbon four byproduct of the steam cracking device and the mixed carbon four byproduct of the FCC device in the prior art. The invention adopts the following steps: 1) adopting an extraction technology to separate and obtain butadiene; 2) adopting etherification technology, and synthesizing MTBE by using isobutene in the raffinate carbon four in the first step; 3) separating water, ether and alcohol in the second etherified C4 by a refining separation technology; 4) carrying out disproportionation reaction on the mixed C4 and ethylene purified in the third step by using an olefin disproportionation technology to produce propylene; 5) the fourth step is that the residual unreacted mixed carbon is recycled as the raw material of the cracking furnace, thus better solving the problem and being applicable to industrial production for increasing the yield of propylene and improving the comprehensive value of mixed carbon.
CN105367366A discloses a method for producing ethylene and propylene by using mixed C4, which mainly solves the problems of low utilization rate and low added value of mixed C4 in the prior art. The invention adopts the following steps: (a) adopting a selective hydrogenation technology to hydrogenate butadiene in the mixed carbon four into mono-olefin; (b) adopting an olefin catalytic cracking technology to catalytically crack the olefins in the mixed C4 into ethylene and propylene; (c) separating unreacted mixed carbon four by a rectification technology; (d) the method adopts the technical scheme that the alkane in the unreacted mixed C4 is removed by adopting the extractive distillation technology, and the residual C tetraalkene is circularly used as the catalytic cracking raw material, so that the problems are well solved, and the method can be used for industrial application for increasing the yield of ethylene and propylene and improving the comprehensive utilization rate of the mixed C4 chemical industry.
However, due to the influence of consumption tax and new government, the industrial chain of mixed aromatics obtained by aromatization of liquefied gas as blended gasoline may decline, the industry of aromatization of liquefied gas is slow, the direct alkylation technology is limited in application due to the pollution problem of the catalyst, the product market of MTBE is severely limited along with the popularization of ethanol gasoline, and isobutene and butene-1 are difficult to separate without an MTBE device. Namely, the mixed C4 in the prior art still has the problems that the large-scale utilization cannot be realized or the utilization rate is low and the like due to the limitation of the process.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a device and a method for comprehensively utilizing mixed C4, which solve the problem that the separation of butene products needs to be separated in advance by reasonably designing the device in the utilization of the mixed C4, and simultaneously crack unreacted components, increase the yield of ethylene and propylene and fully utilize the value of the C4 products.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a device for comprehensive utilization of mixed C4, which comprises a hydroformylation unit, a catalyst separation unit and a light component separation unit which are connected in sequence;
the catalyst solution outlet of the catalyst separation unit is connected with the liquid inlet of the catalyst treatment unit;
the liquid outlet of the catalyst treatment unit is connected with the catalyst inlet of the hydroformylation unit;
and a light component outlet of the light component separation unit is connected with a cracking unit.
The device provided by the invention avoids the separation of butene products through hydroformylation reaction, and simultaneously cracks unreacted components, so that the yield of ethylene and propylene is increased, and the value of carbon four products is fully utilized.
As a preferred technical scheme of the invention, the hydroformylation unit comprises at least 2 tank reactors connected in sequence.
Preferably, the catalyst separation unit comprises a falling film evaporator.
Preferably, the catalyst treatment unit comprises an extraction column.
Preferably, the light component separation unit comprises a rectification column.
Preferably, the liquid outlet of the light component separation unit is connected with a mixed aldehyde separation unit.
Preferably, the mixed aldehyde separation unit comprises a rectification column.
In the invention, 1-butene, 2-butene and isobutene are subjected to a hydroformylation reaction unit to generate n-isovaleraldehyde; the reacted mixture passes through a catalyst separation unit, the catalyst is recycled after being separated, and the reaction product passes through a light component separation unit, and light components such as unreacted butylene and butane are separated and then enter an olefin cracking unit to obtain a product rich in ethylene and propylene; the n-isovaleraldehyde obtained by the light component separation unit passes through the valeraldehyde separation unit to obtain n-valeraldehyde and isovaleraldehyde products.
In a second aspect, the invention provides a method for mixed carbon four comprehensive utilization based on the device in the first aspect, wherein the method comprises the following steps:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, and separating to obtain a light component and a mixed aldehyde product;
(3) and introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit.
In the invention, the mixed C-C raw material is a mixture of olefin and alkane which do not contain butadiene, the olefin is one or more of 1-butene, cis-trans-2-butene and isobutene, and the alkane is one or two of n-butane and isobutane and can also not contain alkane.
As a preferable technical scheme of the invention, the mixed C4 in the step (1) comprises 30-40% of n-butene, 35-45% of isobutene and the balance of butane in percentage by mol.
In the present invention, n-butene in the mixed C.sub.four is 30 to 40% by mole, and may be, for example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the content of isobutylene in the mixed C4 is 35 to 45% by mole, and may be, for example, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, or 45%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the butane comprises n-butane and/or isobutane.
Preferably, the synthesis gas of step (1) comprises carbon monoxide and hydrogen.
Preferably, the molar ratio of carbon monoxide to hydrogen in the synthesis gas in step (1) is 1 (1-1.2), and may be, for example, 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09, 1:1, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:2, etc., but is not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, in step (1), the ratio of the total molar amount of n-butene and isobutene to the molar amount of carbon monoxide is (0.9-1):1, and may be, for example, 0.9:1, 0.91:1, 0.92:1, 0.93:1, 0.94:1, 0.95:1, 0.96:1, 0.97:1, 0.98:1, 0.99:1 or 1:1, but is not limited to the values listed, and other values not listed in this range are equally applicable.
As a preferred technical scheme of the invention, the catalyst in the step (1) is a rhodium-diphosphite system catalyst.
Preferably, the amount of the bisphosphite ligand in the catalyst of step (1) is 0.3 to 0.8 wt% in terms of mass percent, and may be, for example, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, or 0.8 wt%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable. The mass percentage of the bisphosphite ligand means the content thereof in the solution system.
Preferably, the molar ratio of phosphine to rhodium in the catalyst of step (1) is (9-10):1, and may be, for example, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1 or 10:1, without being limited to the values recited, and other values not recited in this range are equally applicable.
As a preferred embodiment of the present invention, the temperature of the reaction in the step (1) is 70 to 100 ℃, and for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃ may be used, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the reaction pressure in step (1) is 1.1 to 1.5MPaG, and may be, for example, 1.1MPaG, 1.15MPaG, 1.2MPaG, 1.25MPaG, 1.3MPaG, 1.35MPaG, 1.4MPaG, 1.45MPaG, or 1.5MPaG, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the residence time of the reactants in the first kettle in the formylation reaction in the step (1) is 2-4h, the residence time in the second kettle is 2-4h, the residence time in the first kettle can be, for example, 2h, 2.5h, 3h, 3.5h or 4h, etc., the residence time in the second kettle can be, for example, 2h, 2.5h, 3h, 3.5h or 4h, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
As a preferred embodiment of the present invention, the pressure for the separation in the step (1) is 0.2 to 0.3MPa, and may be, for example, 0.2MPa, 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, 0.26MPa, 0.27MPa, 0.28MPa, 0.29MPa or 0.3MPa, but is not limited to the values listed above, and other values not listed in this range are also applicable.
Preferably, the temperature for the separation in step (1) is 100-110 ℃, and may be, for example, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃ or 110 ℃, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical scheme of the invention, the light component in the step (2) is treated by a cracking unit to obtain a cracking product.
As a preferable technical scheme of the invention, the mixed aldehyde product in the step (2) is rectified to obtain n-valeraldehyde and isovaleraldehyde.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, separating to obtain a light component and a mixed aldehyde product, and cracking the light component;
(3) introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit;
the reaction temperature in the step (1) is 70-100 ℃, the pressure is 1.1-1.5MPaG, the residence time of reactants in a first kettle in the formylation reaction is 2-4h, and the residence time in a second kettle is 2-4 h.
In the invention, the mixed aldehyde product can be separated into pure n-valeraldehyde and isovaleraldehyde, and a mixture containing more than 80% of n-valeraldehyde and pure isovaleraldehyde can also be obtained according to the requirements of subsequent products.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention designs a new device and a new process aiming at the mixed C4, avoids the separation of butene components through hydroformylation reaction, reduces energy consumption, simultaneously cracks unreacted components, increases the yield of ethylene and propylene, and fully utilizes the value of C4 products.
(2) The invention designs a new device and a new process aiming at the mixed C4, increases the yield of n-isovaleraldehyde through hydroformylation reaction, increases the product chain length of butene, realizes the high-value conversion of C4 products, realizes the high-efficiency utilization of the mixed C4 by utilizing specific reaction parameters, and obviously improves the yield and the purity of valeraldehyde and the utilization rate of the mixed C4.
(3) The process can be used for preparing refinery C4, cracking C four, and byproduct C four in methanol-to-olefin (MTO, MTP and CMTX) process, has strong adaptability to raw materials, provides a path for deep processing and utilization of mixed C4, and is easy to popularize and apply.
Drawings
Fig. 1 is a schematic diagram of a mixed carbon four comprehensive utilization apparatus provided in embodiment 1 of the present invention.
In the figure: a is a hydroformylation unit, a B-catalyst separation unit, a C-catalyst treatment unit, a D-light component separation unit and an E-mixed aldehyde separation unit; an F-cleavage unit;
1-mixing a carbon four raw material, 2-synthetic gas, 3-unreacted light components, reaction products and catalyst mixed liquor, 4-unreacted light components and reaction products mixed liquor, 5-untreated catalyst solution, 6-treated catalyst solution, 7-light components, 8-mixed aldehyde products, 9-n-valeraldehyde, 10-isovaleraldehyde, 11 is purge gas and 12-cracking products.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a device for comprehensive utilization of mixed C4, as shown in FIG. 1, the device comprises a hydroformylation unit A, a catalyst separation unit B and a light component separation unit D which are connected in sequence;
the catalyst solution outlet of the catalyst separation unit B is connected with the liquid inlet of the catalyst treatment unit C;
the liquid outlet of the catalyst treatment unit C is connected with the catalyst inlet of the hydroformylation unit A;
a light component outlet of the light component separation unit D is connected with a cracking unit F;
the hydroformylation unit A is 2 kettle type reactors which are connected in sequence;
the catalyst separation unit B is a falling film evaporator;
the catalyst treatment unit C is an extraction tower;
the light component separation unit D is a rectifying tower;
the liquid outlet of the light component separation unit D is connected with a mixed aldehyde separation unit E;
the mixed aldehyde separation unit E is a rectifying tower.
Application example 1
The application example adopts the device of the embodiment 1, and provides a method for comprehensively utilizing mixed C4, which comprises the following steps:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, separating to obtain a light component and a mixed aldehyde product, and cracking the light component;
(3) and introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit.
The carbon four mixture comprises 35% of n-butene, 40% of isobutene and the balance of butane in percentage by mole, the molar ratio of carbon monoxide to hydrogen in the synthesis gas is 1:1.1, and the ratio of the total molar amount of the n-butene and the isobutene to the molar amount of the carbon monoxide is 1: 1;
the catalyst is a rhodium-diphosphite system catalyst, the diphosphite ligand in the catalyst accounts for 0.5 wt% in mass percentage, and the molar ratio of phosphine to rhodium in the catalyst is 9.5: 1;
the reaction temperature in the hydroformylation unit is 90 ℃, the pressure is 1.3MPaG, the residence time of reactants in the first kettle is 2 hours, and the residence time in the second kettle is 3 hours;
the separation pressure is 0.25MPa, and the separation temperature is 100 ℃; and treating the light component by a cracking unit to obtain a cracking product, and rectifying the mixed aldehyde product to obtain n-valeraldehyde and isovaleraldehyde.
The utilization rate of the obtained mixed C4, the purity and the yield of the aldehyde product are detailed in table 1.
Application example 2
The application example adopts the device of the embodiment 1, and provides a method for comprehensively utilizing mixed C4, which comprises the following steps:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, separating to obtain a light component and a mixed aldehyde product, and cracking the light component;
(3) and introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit.
The content of the mixed C4 is 45% of n-butene, 30% of isobutene and the balance of butane in percentage by mole, the molar ratio of carbon monoxide to hydrogen in the synthesis gas is 1:1, and the ratio of the total molar amount of the n-butene and the isobutene to the molar amount of the carbon monoxide is 0.95: 1;
the catalyst is a rhodium-diphosphite system catalyst, the diphosphite ligand in the catalyst accounts for 0.3 wt% in mass percentage, and the molar ratio of phosphine to rhodium in the catalyst is 10: 1;
the reaction temperature in the hydroformylation unit is 95 ℃, the pressure is 1.5MPaG, the residence time of reactants in the first kettle is 2 hours, and the residence time in the second kettle is 4 hours;
the separation pressure is 0.3MPa, and the separation temperature is 110 ℃; and treating the light component by a cracking unit to obtain a cracking product, and rectifying the mixed aldehyde product to obtain n-valeraldehyde and isovaleraldehyde.
The utilization rate of the obtained mixed C4, the purity and the yield of the aldehyde product are detailed in table 1.
Application example 3
The application example adopts the device of the embodiment 1, and provides a method for comprehensively utilizing mixed C4, which comprises the following steps:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, separating to obtain a light component and a mixed aldehyde product, and cracking the light component;
(3) and introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit.
The carbon four mixture comprises 40% of n-butene, 35% of isobutene and the balance of butane in percentage by mole, the molar ratio of carbon monoxide to hydrogen in the synthesis gas is 1:1.2, and the ratio of the total molar amount of the n-butene and the isobutene to the molar amount of the carbon monoxide is 0.9: 1;
the catalyst is a rhodium-diphosphite system catalyst, the diphosphite ligand in the catalyst accounts for 0.8 wt% in mass percentage, and the molar ratio of phosphine to rhodium in the catalyst is 9: 1;
the reaction temperature in the hydroformylation unit is 100 ℃, the pressure is 1.4MPaG, the residence time of reactants in the first kettle is 4h, and the residence time in the second kettle is 2 h;
the separation pressure is 0.2MPa, and the separation temperature is 100 ℃; and treating the light component by a cracking unit to obtain a cracking product, and rectifying the mixed aldehyde product to obtain n-valeraldehyde and isovaleraldehyde.
The utilization rate of the obtained mixed C4, the purity and the yield of the aldehyde product are detailed in table 1.
Comparative example 1
The difference from application example 1 is only that the molar ratio of carbon monoxide to hydrogen in the synthesis gas is 1:2, and the utilization rate of the obtained mixed carbon four, and the purity and yield of the aldehyde product are detailed in table 1.
Comparative example 2
The difference from application example 1 is that the residence time of the reactants in the formylation reaction in the first kettle is 1h, the residence time in the second kettle is 0.5h, the utilization rate of the obtained mixed C4, and the purity and the yield of the aldehyde product are shown in Table 1.
Comparative example 3
The difference from application example 1 is only that the reaction temperature in the formylation reaction is 60 ℃, the utilization rate of the obtained mixed C4, and the purity and yield of the aldehyde product are detailed in table 1.
Comparative example 4
The only difference from application example 1 is that no cracking device is provided, the unreacted mixed C4 part is sent to be combusted, the utilization rate of the obtained mixed C4, and the purity of the aldehyde product are detailed in Table 1.
TABLE 1 utilization of Mixed C4 and purity of aldehyde product in examples and comparative examples
From the results of the above examples and comparative examples, it can be seen that the present invention employs a redesigned apparatus, and simultaneously employs a redesigned utilization method, and utilizes specific reaction parameters therein to achieve efficient utilization of mixed C4, thereby significantly improving yield and purity of valeraldehyde and utilization of mixed C4. .
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The device for comprehensively utilizing the mixed C4 is characterized by comprising a hydroformylation unit, a catalyst separation unit and a light component separation unit which are sequentially connected;
the catalyst solution outlet of the catalyst separation unit is connected with the liquid inlet of the catalyst treatment unit;
the liquid outlet of the catalyst treatment unit is connected with the catalyst inlet of the hydroformylation unit;
and a light component outlet of the light component separation unit is connected with a cracking unit.
2. The hybrid carbon four integrated utilization apparatus according to claim 1, wherein said hydroformylation unit comprises at least 2 tank reactors connected in series;
preferably, the catalyst separation unit comprises a falling film evaporator;
preferably, the catalyst treatment unit comprises an extraction column;
preferably, the light component separation unit comprises a rectification column;
preferably, a liquid outlet of the light component separation unit is connected with a mixed aldehyde separation unit;
preferably, the mixed aldehyde separation unit comprises a rectification column.
3. A method for comprehensively utilizing mixed C4 is characterized by comprising the following steps:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, separating to obtain a light component and a mixed aldehyde product, and cracking the light component;
(3) and introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit.
4. The method of claim 3, wherein the mixed C4 of step (1) comprises, in mole percent, 30-40% n-butene, 35-45% isobutene, and the balance butane;
preferably, the synthesis gas of step (1) comprises carbon monoxide and hydrogen;
preferably, the molar ratio of carbon monoxide to hydrogen in the synthesis gas in the step (1) is 1 (1-1.2);
preferably, in the step (1), the ratio of the total molar amount of the n-butene and the isobutene to the molar amount of the carbon monoxide is (0.9-1): 1.
5. The process of claim 3 or 4, wherein the catalyst of step (1) is a rhodium-bisphosphite system catalyst;
preferably, the content of the diphosphite ligand in the catalyst in the step (1) is 0.3-0.8 wt% in percentage by mass;
preferably, the molar ratio of phosphine to rhodium in the catalyst in the step (1) is (9-10): 1.
6. The process of any one of claims 3 to 5, wherein the temperature of the reaction of step (1) is from 70 ℃ to 100 ℃;
preferably, the pressure of the reaction of step (1) is 1.1 to 1.5 MPaG;
preferably, the residence time of the reactants in the formylation reaction in the step (1) in the first kettle is 2-4h, and the residence time in the second kettle is 2-4 h.
7. The process according to any one of claims 3 to 6, wherein the pressure of the separation in step (1) is from 0.2 to 0.3 MPa;
preferably, the temperature for the separation in step (1) is 100-110 ℃.
8. The method of any one of claims 3 to 7, wherein the light fraction of step (2) is treated by a cracking unit to obtain a cracked product.
9. The method of any one of claims 3-8, wherein the mixed aldehyde product of step (2) is subjected to rectification to obtain n-valeraldehyde and isovaleraldehyde.
10. A method according to any of claims 3-9, characterized in that the method comprises the steps of:
(1) reacting the mixed C4, the synthesis gas and the catalyst in a hydroformylation unit, then extracting unreacted light components, reaction products and catalyst mixed liquor, and introducing the light components, the reaction products and the catalyst mixed liquor into a catalyst separation unit for separation;
(2) introducing the unreacted light component and the reaction product mixture obtained by separation into a light component separation unit, separating to obtain a light component and a mixed aldehyde product, and cracking the light component;
(3) introducing the catalyst solution obtained by the catalyst separation unit into a catalyst treatment unit, and returning the treated circulating catalyst to the hydroformylation unit;
the reaction temperature in the step (1) is 70-100 ℃, the pressure is 1.1-1.5MPaG, the residence time of reactants in a first kettle in the formylation reaction is 2-4h, and the residence time in a second kettle is 2-4 h.
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