CN116178093A - Alkyne hydrogenation feeding optimization method - Google Patents
Alkyne hydrogenation feeding optimization method Download PDFInfo
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- CN116178093A CN116178093A CN202211619441.0A CN202211619441A CN116178093A CN 116178093 A CN116178093 A CN 116178093A CN 202211619441 A CN202211619441 A CN 202211619441A CN 116178093 A CN116178093 A CN 116178093A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 197
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000005457 optimization Methods 0.000 title claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 abstract description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001273 butane Substances 0.000 abstract description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 27
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 23
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 23
- 150000001993 dienes Chemical class 0.000 description 17
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000005673 monoalkenes Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development 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
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
-
- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an alkyne hydrogenation feeding optimization method, which comprises the steps of changing the feeding mode of a secondary hydrogenation reactor, newly adding an external circulation flow of the secondary hydrogenation reactor, increasing the mass airspeed of the secondary hydrogenation reactor, improving the material distribution in the secondary hydrogenation reactor, enabling hydrogen to fully contact with alkyne-containing carbon four and butadiene, and reducing the reaction of the hydrogen and butene to generate butane; the theoretical hydrogen consumption multiple can reach 1.02-1.10, the hydrogen consumption is greatly reduced, and the material loss is reduced as a whole. Meanwhile, the online chromatograph of the outlet of the first-stage hydrogenation reactor is newly added, and the hydrogen consumption is further reduced on the premise of ensuring the qualified quality of the hydrogenation products by optimizing the hydrogen consumption distribution of the first-stage hydrogenation reactor and the second-stage hydrogenation reactor.
Description
Technical Field
The invention relates to the technical field of chemical production and synthesis, in particular to an optimization method of alkyne hydrogenation feed.
Background
The C4 hydrocarbon is mainly from the processes of catalytic cracking in oil refinery, ethylene preparing device by hydrocarbon cracking, olefin preparing by coal, etc., the main components are n-butane, isobutane, 1-butene, 2-butene, isobutene and butadiene, and the mixture and single component have good industrial utilization value and prospect. At present, the byproduct carbon four of each refining enterprise cannot be integrated together but are processed respectively, so that the scale of a carbon four hydrocarbon utilization device in China is smaller, the technical development capability is poor, and the utilization rate of the carbon four resources of the refining enterprise in China is only 40%.
The butadiene extraction device of the Zhonghai shell can extract and concentrate butadiene and simultaneously can produce a mixed carbon four-material rich in alkyne, and main alkyne components in the material are vinyl acetylene, ethyl acetylene, propyne and the like. Because of the unstable double bond and triple bond structure in the vinyl acetylene structure, the vinyl acetylene is very easy to oxidize in the air to generate explosive peroxide, and is easy to generate polymerization reaction, emit a large amount of heat, and is also unstable to heat and easy to decompose and explode. Therefore, the materials are difficult to treat, and have a certain danger, and the problems of incomplete combustion, black smoke emission, environmental pollution and the like can be caused by the alkyne-containing carbon are caused no matter the alkyne-containing carbon is mixed into civil liquefied gas or the alkyne-containing carbon is directly discharged to a torch for burning. Meanwhile, the olefin content in the material can reach 88wt%, so that the material is a very high-quality and unattainable chemical raw material, and is directly burnt out, thereby causing the waste of resources.
In order to avoid the waste of materials caused by directly discharging the alkyne and the diene materials into the torch for burning, the alkyne is changed into the mono-olefin in a selective hydrogenation mode, so that the dangerous factors of the materials are essentially solved, the harmless purpose is achieved, and the hydrogenation product can be used as the butene raw material of a downstream device by controlling the hydrogenation depth, so that the utilization rate of the materials is improved. Not only eliminates the potential safety hazard of storing the materials, but also carries out high-efficiency resource utilization on the materials.
In order to prevent olefin waste caused by excessive hydrogenation of alkyne and diene, two hydrogenation reactors are used in series in the actual alkyne hydrogenation process, namely alkyne-containing carbon four is subjected to selective hydrogenation through a first-stage hydrogenation reactor, so that most alkyne and diene are converted into mono-olefin, and in order to better control the bed temperature rise of the first-stage hydrogenation reactor, the material at the outlet of the first-stage hydrogenation reactor is partially returned to an inlet, and a water cooler is used for heat extraction; and (3) feeding the rest unconverted part of alkyne and diene after the reaction in the first-stage hydrogenation reactor into the second-stage hydrogenation reactor for hydrogenation, and finally obtaining a qualified hydrogenation product and sending the qualified hydrogenation product to a downstream unit for processing.
However, the above alkyne hydrogenation process still has the following problems: because the material inside the second-stage hydrogenation reactor is unevenly distributed, in order to ensure that the hydrogenation product is qualified, the space velocity of the second-stage hydrogenation reactor of the hydrogenation reactor is increased by adopting a mode of increasing the hydrogen consumption, so that the hydrogen is in contact reaction with acetylene-containing carbon four-butadiene in the second-stage hydrogenation reactor to generate mono-olefin as far as possible, and the situation that butane is generated by the reaction of the hydrogen and mono-olefin to cause excessive loss of the hydrogen and the butene is avoided. However, increasing the amount of hydrogen will cause hydrogen to be excessive and accumulated in the hydrogenation system, so that the pressure of the hydrogenation system is high, and in order to maintain the operating pressure of the hydrogenation system, excessive hydrogen and isobutene of the system need to be discharged as fuel gas, thereby causing a great amount of hydrogen and isobutene to be lost.
Disclosure of Invention
The invention aims to provide an alkyne hydrogenation feeding optimization reaction method, which solves the problem of uneven material distribution in a hydrogenation reactor, reduces the consumption of hydrogen, reduces the loss of hydrogen and isobutene and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
the alkyne hydrogenation feeding optimization method comprises the steps that four raw materials containing alkyne sequentially pass through a first-stage hydrogenation reactor and a second-stage hydrogenation reactor which are connected in series, wherein hydrogenation materials of the first-stage hydrogenation reactor are partially returned to an inlet after passing through a first-stage flash evaporator, and the other part of the hydrogenation materials enter the second-stage hydrogenation reactor to carry out hydrogenation reaction, so that hydrogenation products are obtained; the method is characterized in that: the method also comprises the step of partially recycling the outlet materials of the second-stage hydrogenation reactor to the feed inlet of the second-stage hydrogenation reactor after passing through the second-stage flash tank so as to improve the distribution of the materials in the second-stage hydrogenation reactor and extracting the rest materials.
Further, the flow of the outlet material of the second-stage hydrogenation reactor, which returns to the second-stage hydrogenation reactor after passing through the second-stage flash tank, is adjusted for a plurality of times, and the adjustment range is controlled to be 2t/h-3t/h each time until the flow of carbon four at the inlet of the second-stage hydrogenation reactor is increased to 12t/h-15t/h.
Further, the method comprises the step of increasing the mass space velocity of the secondary hydrogenation reactor to 7-12h -1 The hydrogen consumption is 1.02-1.10 times of the theoretical hydrogen consumption.
Preferably, the radial temperature difference of the middle bed layer of the two-stage hydrogenation reactor is 1-3 ℃.
Further, the method also comprises the step of monitoring the inlet material composition of the first-stage hydrogenation reactor and the outlet product composition of the second-stage hydrogenation reactor in real time by a newly-added online chromatograph.
Further, the method also comprises the step of adjusting the hydrogen consumption of the first-stage hydrogenation reactor and the second-stage hydrogenation reactor.
Preferably, the hydrogen consumption of the first-stage hydrogenation reactor accounts for 90-95% of the total hydrogen consumption.
Preferably, the first-stage hydrogenation reactor process conditions: the feeding temperature is 30-35 ℃, the hot spot temperature is 40-75 ℃, and the operating pressure is 0.3-1.8 MPa.
Preferably, the two-stage hydrogenation reactor process conditions: the feeding temperature is 30-35 ℃, the hot spot temperature is 40-75 ℃, and the operating pressure is 0.3-1.7 MPa.
Preferably, the pressure of the first-stage flash evaporator is 0.3MPa to 1.6MPa, and the pressure of the second-stage flash tank is 0.3MPa to 1.6MPa.
In summary, the technical scheme of the invention has the following beneficial effects:
1. according to the invention, through the newly added external circulation flow of the two-stage hydrogenation reactor, the feeding mode of the two-stage hydrogenation reactor is changed, the material distribution in the two-stage hydrogenation reactor is improved, so that hydrogen fully contacts with acetylene-containing carbon four and butadiene, and the reaction of the hydrogen and butene is reduced to generate butane; meanwhile, the theoretical hydrogen consumption multiple can reach 1.02-1.10, the hydrogen consumption is greatly reduced, and the material loss is integrally reduced.
2. Meanwhile, the online chromatograph of the outlet of the first-stage hydrogenation reactor is newly added, and the hydrogen consumption and loss are further improved by optimizing the hydrogen consumption distribution of the first-stage hydrogenation reactor and the second-stage hydrogenation reactor.
Drawings
FIG. 1 is a schematic diagram of the alkyne hydrogenation reaction scheme of the present invention;
FIG. 2 is a graph of V1/V2 operating temperature versus pressure for example 1;
FIG. 3 is a graph of V1/V2 operating temperature versus pressure for comparative example 1.
The reference numerals in the drawings are: hydrogen feed to the 1# 1 hydrogenation reactor; 2-four feeds containing alkyne carbon; hydrogen feed to 3-2 # hydrogenation reactor; 4-hydrogenation product; r1 is a one-stage hydrogenation reactor; r2 is a two-stage hydrogenation reactor; v1 is a one-stage flash tank; a V2 two-stage flash tank; e1-a hydrogenation circulation cooler; e2-a series reaction cooler; e3—a hydrogenation product cooler; a P1-1 # hydrogenation circulating pump; p2-hydrogenation product booster pump; feeding mixer of M1-1 # hydrogenation reactor; feeding mixer of M2-2 # hydrogenation reactor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, but the scope of protection of the present invention is not limited.
The four-selective hydrogenation of acetylenic carbon in the invention mainly relates to the following reactions:
(1) Hydrogenation of vinyl acetylene: CH (CH) 2 ＝CH-C≡CH+2H 2 →CH 2 -CH-CH＝CH 2 ；
(2) Hydrogenation of 1, 3-butadiene: CH (CH) 2 ＝CH-CH＝CH 2 +H 2 →CH 3 -CH 2 -CH＝CH 2 ；
(3) Hydrogenation of 1, 2-butadiene: CH (CH) 2 ＝C＝CH-CH 2 +H 2 →CH 3 -CH 2 -CH＝CH 2 、CH 2 ＝C＝CH-CH 2 +H 2 →CH 3 -CH 2 ＝CH-CH 2
(4) Hydrogenation of ethyl acetylene: CH (CH) 3 -CH 2 -C≡CH+H 2 →CH 3 -CH 2 -CH＝CH 2 ；
(5) Hydrogenation of butene: CH (CH) 3 -CH 2 -CH＝CH 2 +H 2 →CH 3 -CH 2 -CH 2 -CH 3 、CH 3 -CH＝CH-CH 3 +H 2 →CH 3 -CH 2 -CH 2 -CH 3
The above reactions (1) to (4) are main reactions, and the above reaction (5) is a side reaction.
Wherein the theoretical hydrogen consumption multiple is the molar ratio multiple of hydrogen to carbon, namely 1mol C 4 H 4 And 2molH 2 The reaction produced 1molC 4 H 8 、1molC 4 H 6 And 1mol H 2 The reaction produced 1molC 4 H 8 、1molC 4 H 8 And 1mol H 2 The reaction produced 1molC 4 H 10 。
In the actual reaction process, the hydrogen consumption is required to be excessive to ensure that the alkyne and diene content in the hydrogenated product is below 500ppm, but the theoretical hydrogen consumption is excessive, so that butane is produced by the reaction of butene and hydrogen, alkane increment in the hydrogenated product is excessive, hydrogen is wasted, and butene loss is caused, so that the theoretical hydrogen consumption is required to be controlled as low as possible under the condition of ensuring that the alkyne and diene content in the hydrogenated product is below 500 ppm.
Referring to fig. 1, the present invention provides an alkyne hydrogenation feed optimization process including, but not limited to: feeding 2 of the raw material containing acetylenic carbon four and hydrogen feed 1 of a 1# hydrogenation reactor into a first-stage hydrogenation reactor R1 for selective hydrogenation reaction. The outlet material of the first-stage hydrogenation reactor R1 is sent to a first-stage flash tank V1, and the material coming out of the first-stage flash tank is partially sent to the inlet of the first-stage hydrogenation reactor R1 through a hydrogenation circulating pump P1.
In order to make alkyne and diene selective hydrogenation more abundant, the product material of first section hydrogenation reactor is sent into second section hydrogenation reactor R2 with 2# hydrogenation reactor hydrogen feeding 3 and is carried out selective hydrogenation. The hydrogenation product of the second-stage hydrogenation reactor R2 enters a second-stage flash tank V2, and then the hydrogenation product 4 is produced by a hydrogenation product booster pump.
And part of outlet materials of the second-stage flash tank V2 are sent to an inlet of the second-stage hydrogenation reactor R2 through external circulation, so that the mass airspeed of the second-stage hydrogenation reactor R2 is increased, the material distribution in the second-stage hydrogenation reactor R2 is optimized, hydrogen is contacted with acetylene-containing carbon four and butadiene in the second-stage hydrogenation reactor R2 to react as much as possible to generate mono-olefin, the reaction of the hydrogen and mono-olefin to generate butane is avoided, and the problem of overlarge loss of the hydrogen and the butene is solved.
And (3) newly adding an online chromatograph to track the change condition of each component of the hydrogenation product in real time, reasonably distributing the hydrogen consumption of the first-stage hydrogenation reactor R1 and the second-stage hydrogenation reactor R2 according to the change condition of the content of each component in the hydrogenation product, and further reducing the hydrogen consumption and gradually reducing the flow of noncondensable gas of the second-stage flash tank V2 to the fuel gas buffer tank under the condition of ensuring the quality of the hydrogenation product.
Preferably, the flow of the outlet material of the second-stage hydrogenation reactor, which returns to the second-stage hydrogenation reactor after passing through the second-stage flash tank, is adjusted for a plurality of times, and the adjustment amplitude is controlled to be 2t/h-3t/h each time until the flow of carbon four at the inlet of the second-stage hydrogenation reactor is increased to 12t/h-15t/h.
Preferably, the mass space velocity of the two-stage hydrogenation reactor is increased to 7-12h -1 The hydrogen consumption is 1.02-1.10 times of the theoretical hydrogen consumption.
Preferably, the radial temperature difference of the middle bed layer of the two-stage hydrogenation reactor is 1-3 ℃.
Preferably, the process conditions of the first-stage reactor R1 are that the feeding temperature is 30-35 ℃, the hot spot temperature is 40-75 ℃, and the reaction pressure is 0.3-1.8 MPa.
Preferably, the process conditions of the two-stage hydrogenation reactor R2: the feeding temperature is 30-35 ℃, the hot spot temperature is 40-75 ℃, and the operating pressure is 0.3-1.7 MPa.
Preferably, the pressure V1 of the primary flash steam is 0.3MPa to 1.6MPa, and the pressure of the secondary flash tank is 0.3MPa to 1.6MPa.
The following is a further illustration of an alkyne hydrogenation feed optimization process of the present invention in conjunction with the examples.
Example 1
The method comprises the steps of (1) washing 3t/h of acetylene-containing carbon four raw materials with 14.48 weight percent of vinyl acetylene content, 14.34 weight percent of total ethyl acetylene content and diene content, purifying the acetylene-containing carbon four raw materials by water, then conveying the raw materials to a first-stage hydrogenation reactor R1 for selective hydrogenation reaction, controlling the external circulation volume of the first-stage hydrogenation reactor R1 to be 90t/h, controlling the inlet temperature to be 32 ℃, controlling the operating pressure to be 0.9MPa, controlling the external circulation volume of a second-stage hydrogenation reactor R2 to be 10t/h, controlling the inlet temperature to be 32 ℃, controlling the operating pressure to be 0.8MPa, controlling the hydrogen consumption to be 1.01 times of the theoretical hydrogen consumption, controlling the total of alkyne and diene content of hydrogenation products to be 100ppm after hydrogenation, and controlling the alkane increment to be 5.86 weight percent. The temperature and pressure change curves of the first-stage flash tank V1 and the second-stage flash tank V2 are shown in FIG. 2.
Example 2
The method comprises the steps of (1) washing 4t/h of acetylene-containing carbon four, wherein the vinyl acetylene content in the acetylene-containing carbon four raw material is 15.08wt%, the sum of the ethyl acetylene content and the diene content is 12.39wt%, purifying the acetylene-containing carbon four raw material by water, then conveying the purified acetylene-containing carbon four raw material to a first-stage hydrogenation reactor R1 for selective hydrogenation reaction, controlling the external circulation volume of the first-stage hydrogenation reactor R1 to be 95t/h, controlling the inlet temperature to be 32 ℃, controlling the operating pressure to be 0.9MPa, controlling the external circulation volume of a second-stage hydrogenation reactor R2 to be 8t/h, controlling the inlet temperature to be 32 ℃, controlling the operating pressure to be 0.8MPa, controlling the hydrogen consumption to be 1.03 times of the theoretical hydrogen consumption, enabling the sum of the alkyne content and the diene content of hydrogenation products to be zero after hydrogenation, and enabling the alkane increment to be 6.20wt%.
Example 3
The method comprises the steps of (1) washing 5t/h of acetylene-containing carbon four, wherein the vinyl acetylene content in the acetylene-containing carbon four raw material is 15.38wt%, the sum of the ethyl acetylene content and the diene content is 13.1wt%, purifying the acetylene-containing carbon four raw material by water, then conveying the purified acetylene-containing carbon four raw material to a first-stage hydrogenation reactor R1 for selective hydrogenation reaction, controlling the external circulation amount of the first-stage hydrogenation reactor R1 to be 100t/h, the inlet temperature to be 32 ℃, the operating pressure to be 0.9MPa, the external circulation amount of a second-stage hydrogenation reactor R2 to be 6t/h, the inlet temperature to be 32 ℃, the operating pressure to be 0.8MPa, the hydrogen consumption to be 1.08 times of the theoretical hydrogen consumption, the sum of the alkyne content and the diene content of a hydrogenation product after hydrogenation to be 80ppm, and the alkane increment to be 5.95wt%.
Example 4
The method comprises the steps of (1) washing 6t/h of acetylene-containing carbon four raw materials with 15.32 weight percent of vinyl acetylene content, 15.62 weight percent of total ethyl acetylene content and diene content, purifying the acetylene-containing carbon four raw materials by water, then conveying the raw materials to a first-stage hydrogenation reactor R1 for selective hydrogenation reaction, controlling the external circulation volume of the first-stage hydrogenation reactor R1 to be 110t/h, the inlet temperature to be 34 ℃, the operating pressure to be 0.9MPa, the external circulation volume of a second-stage hydrogenation reactor R2 to be 8t/h, the inlet temperature to be 33 ℃, the operating pressure to be 0.8MPa, the hydrogen consumption to be 1.03 times of the theoretical hydrogen consumption, the total of the alkyne and diene content of a hydrogenation product after hydrogenation to be 20ppm, and the alkane increment to be 5.97 weight percent.
Example 5
The method comprises the steps of carrying out selective hydrogenation reaction on 7t/h of acetylene-containing carbon four, wherein the vinyl acetylene content in the acetylene-containing carbon four raw material is 15.68wt%, the sum of the ethyl acetylene content and the diene content is 13.31wt%, the acetylene-containing carbon four raw material is washed and purified and then is sent to a first-stage hydrogenation reactor R1, the external circulation volume of the first-stage hydrogenation reactor R1 is controlled to be 120t/h, the inlet temperature is 34 ℃, the operating pressure is 0.9MPa, the external circulation volume of a second-stage hydrogenation reactor R2 is controlled to be 5t/h, the inlet temperature is 33 ℃, the operating pressure is 0.8MPa, the hydrogen consumption is 1.1 times of the theoretical hydrogen consumption, the sum of the acetylene content and the diene content of a hydrogenation product is 10ppm after hydrogenation, and the alkane increment is 7.59wt%.
Comparative example 1
The method comprises the steps of (1) washing 3t/h of acetylene-containing carbon four raw materials with water, wherein the total content of vinyl acetylene and ethylene is 13.53wt%, the total content of ethylene and ethylene is 13.80wt%, the acetylene-containing carbon four raw materials are purified and then are sent to a hydrogenation reactor for selective hydrogenation reaction, the R1 external circulation amount is controlled to be 90t/h, the inlet temperature is 32 ℃, the operating pressure is 0.9MPa, the R2 external circulation amount is controlled to be 0t/h, the inlet temperature is 32 ℃, the operating pressure is 0.8MPa, the hydrogen consumption is 1.2 times of the theoretical hydrogen consumption, the total content of ethylene and ethylene which are hydrogenation products is 400ppm, and the alkane increment is 7.92wt%. The temperature and pressure change curves of the first-stage flash tank V1 and the second-stage flash tank V2 are shown in FIG. 3.
As can be seen from fig. 3, when the external circulation amount of the second-stage hydrogenation is 0, the operating pressure of the first-stage flash tank V1 and the operating temperature of the first-stage flash tank V1 are in positive correlation, which indicates that the content of noncondensable gas in the first-stage flash tank V1 is low, and hydrogen is substantially completely reacted in the first-stage hydrogenation reactor R1; the operating pressure of the second-stage flash tank V2 does not change obviously along with the change of the operating temperature of the second-stage flash tank V2, which indicates that the content of noncondensable gas in the second-stage flash tank V2 is more, and hydrogen gas cannot completely participate in the reaction in the second-stage hydrogenation reactor R2.
As can be seen from fig. 2, when the external circulation amount of the secondary hydrogenation is 10, the temperature and pressure of the secondary flash tank V2 are lower than V1, and the operating pressure of the secondary flash tank V2 is in positive correlation with the operating temperature, which indicates that the hydrogen is substantially reacted in the secondary hydrogenation reactor R2, so that the process of feeding the noncondensable gas in V2 to the fuel gas buffer tank can be closed to reduce the isobutene loss.
The results show that by establishing the secondary hydrogenation external circulation, the mass space velocity of the materials in the secondary hydrogenation reactor R2 is increased, the distribution of the acetylene-containing carbon four and the hydrogen in the catalyst bed layer of the secondary hydrogenation reactor R2 is improved, so that the hydrogen and the acetylene-containing carbon four are fully contacted on the active surface of the catalyst, the hydrogen can fully participate in the reaction in the secondary hydrogenation reactor R2, and the hydrogen consumption of the secondary hydrogenation reactor R2 and the noncondensable gas discharge amount of the secondary flash tank V2 are reduced.
The process conditions and results corresponding to examples 1-5 and comparative example 1 are shown in Table 1:
TABLE 1
As can be seen from Table 1, by increasing the external circulation amount of the two-stage hydrogenation, the theoretical hydrogen consumption is reduced from 1.2 to 1.01-1.10 after being multiplied, and the C in the hydrogenation product 4 H 4 And C 4 H 6 The content and the alkane increment are in the qualified range, which shows that the hydrogen consumption and the hydrogen loss can be reduced while the qualification of the hydrogenated product is ensured by increasing the external circulation quantity of the second-stage hydrogenation.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (10)
1. The alkyne hydrogenation feeding optimization method comprises the steps that four raw materials containing alkyne sequentially pass through a first-stage hydrogenation reactor and a second-stage hydrogenation reactor which are connected in series, wherein hydrogenation materials of the first-stage hydrogenation reactor are partially returned to an inlet after passing through a first-stage flash evaporator, and the other part of the hydrogenation materials enter the second-stage hydrogenation reactor to carry out hydrogenation reaction, so that hydrogenation products are obtained; the method is characterized in that: the method also comprises the step of partially recycling the outlet materials of the second-stage hydrogenation reactor to the feed inlet of the second-stage hydrogenation reactor after passing through the second-stage flash tank so as to improve the distribution of the materials in the second-stage hydrogenation reactor and extracting the rest materials.
2. A process for optimizing alkyne hydrogenation feed as claimed in claim 1 wherein: the flow of the outlet material of the second-stage hydrogenation reactor, which returns to the second-stage hydrogenation reactor after passing through the second-stage flash tank, is adjusted for a plurality of times, and the amplitude of each adjustment is controlled to be 2t/h-3t/h until the flow of the carbon four at the inlet of the second-stage hydrogenation reactor is increased to 12t/h-15t/h.
3. A process for optimizing alkyne hydrogenation feed as claimed in claim 2 wherein: comprises the step of increasing the mass space velocity of the secondary hydrogenation reactor to 7-12h -1 The hydrogen consumption is 1.02-1.10 times of the theoretical hydrogen consumption.
4. A process for optimizing alkyne hydrogenation feed according to any one of claims 1 to 3 wherein: the radial temperature difference of the middle bed layer of the two-stage hydrogenation reactor is 1-3 ℃.
5. A process for optimizing alkyne hydrogenation feed according to any one of claims 1 to 3 wherein: the method also comprises the step of monitoring the inlet material composition of the first-stage hydrogenation reactor and the outlet product composition of the second-stage hydrogenation reactor in real time by a newly-added online chromatograph.
6. The alkyne hydrogenation feed optimization method according to claim 5, wherein: the method also comprises the step of adjusting the hydrogen consumption of the first-stage hydrogenation reactor and the second-stage hydrogenation reactor.
7. The alkyne hydrogenation feed optimization method of claim 6, wherein: the hydrogen consumption of the first-stage hydrogenation reactor accounts for 90-95% of the total hydrogen consumption.
8. A process for optimizing alkyne hydrogenation feed according to any one of claims 1 to 3 wherein: the technological conditions of the first-stage hydrogenation reactor are as follows: the feeding temperature is 30-35 ℃, the hot spot temperature is 40-75 ℃, and the reaction pressure is 0.3-1.8 MPa.
9. A process for optimizing alkyne hydrogenation feed according to any one of claims 1 to 3 wherein: the process conditions of the two-stage hydrogenation reactor are as follows: the feeding temperature is 30-35 ℃, the hot spot temperature is 40-75 ℃, and the operating pressure is 0.3-1.7 MPa.
10. A process for optimizing alkyne hydrogenation feed according to any one of claims 1 to 3 wherein: the pressure of the first-stage flash evaporator is 0.3MPa-1.6MPa, and the pressure of the second-stage flash tank is 0.3MPa-1.6MPa.
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