CN115011376A - Method for separating alpha-olefin by coupling adsorption distillation and olefin of Fischer-Tropsch light fraction oil - Google Patents
Method for separating alpha-olefin by coupling adsorption distillation and olefin of Fischer-Tropsch light fraction oil Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 100
- 239000004711 α-olefin Substances 0.000 title claims abstract description 65
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000008878 coupling Effects 0.000 title claims abstract description 8
- 238000010168 coupling process Methods 0.000 title claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 8
- 238000004821 distillation Methods 0.000 title claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 239000003921 oil Substances 0.000 claims description 35
- 238000012856 packing Methods 0.000 claims description 28
- 238000007670 refining Methods 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 230000000274 adsorptive effect Effects 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 abstract description 21
- 239000001301 oxygen Substances 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 19
- 238000010992 reflux Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000000470 constituent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- -1 comprises alcohol Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating alpha-olefin by coupling Fischer-Tropsch light distillate oil adsorption rectification with olefin. Cutting the Fischer-Tropsch synthesis light distillate to obtain C4-C10 cut segments; firstly, deeply removing organic oxygen-containing compounds of C4-C10 fractional segments by a simulated moving bed, a fixed bed or other adsorption separation processes; then, the alkane and the alkene in the deoxidized C4-C10 distillate oil are accurately separated by an adsorption rectification technology to obtain the high-purity alpha-alkene. The adsorption rectification technology is coupled with the advantages of rectification and adsorption separation technologies, the adsorption and the rectification technologies cooperate with each other to realize adsorption effect, finally, the fraction is separated from alkane and olefin, and then the high-purity target product alpha-olefin is obtained through deep rectification. Compared with the prior art for separating the alkane and the alkene from the Fischer-Tropsch oil, the method breaks through the barrier of the prior art, realizes the accurate separation of similar fraction products, improves the separation purity of the alpha-olefin and improves the added value of the product.
Description
Technical Field
The invention relates to the field of olefin preparation, in particular to a separation method for separating alpha-olefin from Fischer-Tropsch synthesis light distillate oil by an adsorption rectification coupling separation technology.
Background
Alpha-olefin is mono-olefin with double bond at the end of molecular chain, is an important raw material in petrochemical industry, can be used as comonomer, surfactant synthetic intermediate, plasticizer alcohol, synthetic lubricating oil, oil additive and the like, and has wide application. At present, alpha-olefin is mainly produced by ethylene oligomerization reaction, the process flow is simple, but the byproducts are more, the energy consumption is higher, and the economical efficiency is poor. A large amount of alpha-olefin exists in Fischer-Tropsch synthesis light distillate oil, at present, the Fischer-Tropsch oil is mostly produced by hydrotreating or directly used as a primary chemical material, and the olefin component is utilized at a low value. Therefore, the invention is provided, the alpha-olefin in the Fischer-Tropsch oil is separated by adsorption, rectification and separation, and the alpha-olefin is used as an olefin product with high added value, thereby improving the economic benefit of enterprises.
The components in the industrial Fischer-Tropsch synthesis oil product are complex and comprise alpha-olefin, normal alkane, and oxygen-containing compounds such as alcohol, ketone, aldehyde, ester and the like. The oxygen-containing compound is a toxic substance in the adsorption rectification process, so the deoxidation process is added before the adsorption rectification step, and the oxygen-containing compound in the Fischer-Tropsch oil is completely removed. Meanwhile, the Fischer-Tropsch oil component has azeotropy, the conventional rectification is difficult to realize accurate separation, and the energy consumption is higher.
Patent CN111100683A describes a method for separating long-chain alkane and olefin from fischer-tropsch synthetic oil, in which an oxygen-containing compound is adsorbed by a pre-adsorption tower, and then alpha-olefin and alkane are selectively separated by a simulated moving bed system, so as to obtain an alpha-olefin-rich component and an alkane-rich component, which are respectively sent to a rectification unit. The alpha-olefin and alkane products are obtained by rectification separation and recycling of the desorbent.
Patent CN106753546A describes a method for refining fischer-tropsch synthesis light distillate oil. Firstly, removing metal ion impurities and partial oxygen-containing compounds through a solid phase adsorption unit; and then the residual oxygen-containing compounds in the Fischer-Tropsch synthesis light distillate oil are removed through extraction refining, separation, extractant refining and recovery units in sequence, so that the refining of the Fischer-Tropsch synthesis light distillate oil is realized.
The patent CN109652111A describes an apparatus and a method for separating olefins from fischer-tropsch synthesis oil, which separates alkanes, olefins and oxygen-containing compounds in fischer-tropsch synthesis oil at one time by an apparatus of an extractive distillation dividing wall column, and the extractant is N, N-dimethylformamide. After separation by the bulkhead tower, the extractant and the oxygen-containing compound are mixed and enter a solvent recovery tower for rectification separation, and the extractant is recovered and reused.
Therefore, the prior art for separating olefin has the problems of long process flow and high industrial cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for separating alpha-olefin by Fischer-Tropsch synthesis light distillate oil adsorption rectification coupling, which does not need the use of a desorbent, simplifies the process flow, reduces the industrialization cost and can realize the high-efficiency separation of the alpha-olefin in the Fischer-Tropsch synthesis light distillate oil.
The invention relates to a method for separating alpha-olefin by coupling Fischer-Tropsch light fraction oil adsorption rectification with olefin, which comprises one or more adsorption rectification towers, wherein the packing in the adsorption rectification towers is adsorption packing with olefin adsorption capacity; the adsorption filler is one or more of molecular sieve, modified molecular sieve, silicon oxide, modified silicon oxide, aluminum oxide and modified aluminum oxide; the operation temperature is 50-180 ℃ at the top of the tower, 100-200 ℃ at the bottom of the tower, 0.01-0.5MPa at the top of the operation pressure tower, and 5-80 theoretical plates, continuous or intermittent Fischer-Tropsch synthesis light fraction oil separation is carried out, a saturated hydrocarbon product with low olefin content is at the top of the tower, and a high-purity alpha-olefin product is at the bottom of the tower.
The adsorption packing in the adsorption rectification tower is regular packing, and preferably one or more of Raschig ring packing, theta ring packing and pall ring packing.
The adsorption rectification tower is preferably an adsorption rectification tower containing a plurality of side draws, products of different distillation sections are drawn, and preferably, the side draws are divided into two parts.
The material of the adsorption filler is preferably one or more of molecular sieve with acid center, silicon oxide and aluminum oxide.
The material for adsorbing the filler is preferably NH 3 The desorption temperature of the acid center in the TPD analysis is 120-300 ℃, preferably 200-250 ℃.
And (3) enabling the product obtained by the adsorption rectifying tower to enter an olefin refining unit, wherein the olefin refining unit consists of a plurality of olefin refining rectifying towers, the olefin product is obtained at the tower top, and the alkane product is obtained at the tower bottom.
The temperature of the top of the adsorption rectification tower is 80-150 ℃, the temperature of the bottom of the adsorption rectification tower is 180-200 ℃, the pressure of the top of the adsorption rectification tower is 0.01-0.2 MPa, and the number of theoretical plates is 40-60.
The purity of the alpha-olefin product is more than or equal to 99 percent, preferably more than or equal to 99.2 percent, and the yield of the alpha-olefin is more than or equal to 85 percent, preferably more than or equal to 90 percent.
Compared with the prior art, the invention has the beneficial effects that: the adsorption and rectification processes are coupled, a desorbent is not required to be used, the process flow is simplified, the industrial cost is reduced, the efficient separation of alpha-olefin in Fischer-Tropsch synthesis light distillate oil can be realized, the adsorbent packing has long service cycle, the rectification energy consumption is low, the olefin separation efficiency is high, and a more economical, simple and feasible method is provided for deep processing and other applications of the Fischer-Tropsch synthesis oil alpha-olefin.
Drawings
FIG. 1 is a schematic process flow diagram of a Fischer-Tropsch light fraction oil adsorption rectification coupling olefin separation method.
In the figure: 1. a simulated moving bed apparatus; 2. an extract rectifying tower; 3. a raffinate rectification column; 4. an adsorption rectification column; 5. C4-C7 alkane-alkene mixture rectifying tower; 6. C6-C10 alkane-alkene mixture rectifying tower.
FIG. 2 is a process flow of an adsorption distillation tower of the Fischer-Tropsch light distillate adsorption distillation coupled olefin separation method of the invention.
In the figure: 401 is a special packing for the adsorption rectification column.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention relates to a separation method for separating alpha-olefin from Fischer-Tropsch synthesis light distillate oil. In the process, Fischer-Tropsch synthesis light distillate oil is used as a raw material and comprises C4-C10 alkane, alpha-olefin, other olefin, oxygen-containing compound and the like.
If the alpha-olefin is separated from the Fischer-Tropsch synthesis light distillate oil, the Fischer-Tropsch synthesis light distillate oil is firstly subjected to rectification cutting to obtain a fraction of C4-C10, wherein the olefin mass fraction cannot be lower than 10%, and the preferred mass fraction is 30-70%.
The light Fischer-Tropsch synthesis oil after cutting generally contains 1-10% of oxygen-containing compounds, on one hand, the oxygen-containing compounds have far greater polarity than alkane and olefin, and are preferentially adsorbed in the adsorption rectifying tower, so that the separation performance of the adsorption rectifying tower is influenced; on the other hand, the oxygen-containing compound mainly comprises alcohol, and can be recycled after adsorption and separation by the simulated moving bed. Therefore, the C4-C10 fraction section needs to be sent to an adsorption deoxidation unit to deeply remove oxygen-containing compounds, and the oxygen-containing compounds of the deoxidized oil product are ensured to be less than 10 microgram/gram.
And subsequently, the material without the oxygen-containing organic compound is sent into an adsorption rectification unit, and alkane and alkene components with different carbon numbers are selectively separated. And (3) collecting four streams of materials from the adsorption rectifying tower, collecting C4-C5 paraffin-rich components from the tower top, and collecting C8-C10 alpha-olefin-rich components from the tower bottom, wherein the alpha-olefin purity is more than or equal to 99 percent, preferably more than or equal to 99.5 percent. Two mixtures consisting of alkane and olefin with different carbon numbers are extracted in the middle and sent to a rectification refining unit to obtain a C4-C5 alpha-olefin-rich component and a C6-C7 alpha-olefin-rich component, wherein the purity of the alpha-olefin is more than or equal to 99 percent, and preferably more than or equal to 99.5 percent. The alkane-rich component obtained after rectification can be used for producing fuel oil, lubricating oil or special solvent oil.
The present invention will be described in detail below with reference to the accompanying drawings.
The technological process of separating alpha-olefin from Fischer-Tropsch light fraction oil of C4-C10 is shown in figure 1, and the Fischer-Tropsch synthesis light fraction oil raw material is introduced into a simulated moving bed 1 in an adsorption deoxidation unit for adsorption separation to remove oxygen-containing compounds and reduce the concentration to below 10 mu g/g. The deoxidized material is pumped into an adsorption rectifying tower 4 by a pump, after adsorption, rectification and separation, C4-C5 alkane-rich components are obtained at the tower top, C8-C10 alpha-olefin-rich components are obtained at the tower bottom, a mixture of C6-C7 alkane and C4-C5 olefin is obtained at the side line 1 and is separated in a rectifying tower 5, and a mixture of C8-C10 alkane and C6-C7 olefin is obtained at the side line 2 and is separated in a rectifying tower 6. The alpha-olefin components with high purity of C4-C5 and C6-C7 and the alkane-rich components with high purity of C6-C7 and C8-C10 are obtained after rectification. The present invention is further illustrated by the following examples, but is not limited thereto.
Example 1
The adsorption deoxidation process adopts a simulated moving bed and is formed by connecting 12 columns in series, wherein deoxidation adsorbents are filled in the columns, and the adsorbents are silica gel materials. The 12 th column is connected with the 1 st column through a circulating pump to form material circulation, and materials can be introduced or discharged at the joint of the columns. The number of adsorption columns required for each stage of adsorption separation was set as follows: 3 adsorption columns are arranged between the raw material inlet and the raffinate outlet and are used as adsorption areas; 2 adsorption columns are arranged between the raffinate outlet and the desorbent inlet and are isolation areas; 3 adsorption columns are arranged between the desorbent inlet and the extract outlet and are used as desorption areas; 1 adsorption column is arranged between the extract outlet and the raw material inlet, and is a refining area. At regular intervals, the material inlet and the material outlet are pushed by 1 column along the direction from the material inlet to the raffinate outlet, and so on.
The light distillate oil of C4-C10 enters a simulated moving bed for adsorption deoxidation, the operation temperature is 80 ℃, the proportion of a desorbent to the raw material is 1.5, and the positions of the feed and discharge ports are switched once every 800 seconds, namely, the feed and discharge ports are pushed by 1 column along the direction from the raw material inlet to the raffinate outlet. After the simulated moving bed adsorption deoxidation, the extract and the raffinate respectively enter a rectifying tower for desorbent recycling. The extract tower is a packed tower, the packing is pall rings, the total number of tower plates is 30, the feeding position is at the 15 th tower plate, the operating pressure is 1atm, and the mass reflux ratio is 0.9; the raffinate tower is also a packed tower, the total number of tower plates is 70, the feeding position is the 30 th tower plate, the operating pressure is 1atm, and the mass reflux ratio is 1.8.
The compositions of the products separated by the adsorption and deoxidation process are shown in Table 2, the content of oxygen-containing compounds in the obtained C4-C10 alkane and alkene is less than 10 mu g/g, and the yield reaches 99 percent.
TABLE 1 purity of the components of the streams after adsorption deoxygenation
| C 4 -C 10 Alkane alkene | Oxygen-containing compound | |
| Raw materials wt. -%) | 96.000 | 4.000 |
| Extract tower top wt. -%) | 19.340 | 80.670 |
| % by weight of the raffinate column vessel | 99.999 | 0.001 |
C4-C10 alkane and olefin enter an adsorption rectification tower for further separation after adsorption and deoxidation, the adsorption rectification tower is filled with adsorption filler to ensure that light and heavy components are fully separated, and the adsorption filler is in a theta ring shape and adopts a 13X molecular sieve. The total plate number of the adsorption and rectification tower is 85, 35 tower plates of the adsorption section, 20 tower plates of the rectification section and 25 tower plates of the stripping section. C4-C10 alkane and olefin raw materials enter at a 35 th tower plate (the middle part of an adsorption section), the operation pressure at the top of the tower is 1atm, the mass reflux ratio is 2.5, the temperature at the top of the tower is 45 ℃, and the temperature at the bottom of the tower is 200 ℃. One stream, mainly consisting of a mixture of C6-C7 alkane and C4-C5 alkene, is taken out from the side of the tray 12 and named as side line 1, and the other stream, mainly consisting of a mixture of C8-C10 alkane and C6-C7 alkene, is taken out from the side of the tray 72 and named as side line 2. After adsorption, rectification and separation, the purity of each product is shown in table 3. The purity of the alpha-olefin in the tower bottom C8-C10 reaches more than 99.8 wt.%, and the yield reaches 95%. And two streams of the side stream are directly fed into a rectification refining unit for further processing.
TABLE 213X molecular Sieve physicochemical Properties
TABLE 3 purity of the components of the respective streams after adsorptive rectification
The rectification refining unit adopts two rectifying towers to respectively process two material flows of a lateral line 1 and a lateral line 2, the material flow of the lateral line 1 enters a rectifying tower 5, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower A is 45, the operating pressure at the top of the tower is 1atm, the feeding position is the 20 th plate, and the mass reflux ratio is 1.5. The material flow in the lateral line 2 enters a rectifying tower 6, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower B is 55, the operating pressure is 1atm, the feeding position is the 30 th plate, and the mass reflux ratio is 2.3. After rectification refinement, the product stream component purities are shown in tables 3 and 4. The purity of the C4-C5 alpha-olefin product can reach 99.8 wt.%, the yield reaches 94%, the purity of the C6-C7 alpha-olefin product can reach 99.8 wt.%, and the yield reaches 92%.
TABLE 4 purity of the constituents of the various streams of the rectification column 5
TABLE 5 purity of the constituents of the various streams of the rectification column 6
| Raw material wt. -%) | Tower top wt. -%) | Column bottom wt. -%) | |
| C 4 -C 5 Alkane(s) | 0 | 0 | 0 |
| C 6 -C 7 Alkane(s) | 0.1 | 0.02 | 0 |
| C 8 -C 10 Alkane(s) | 44.20 | 0 | 83.79 |
| C 4 -C 5 Alpha-olefins | 0 | 0 | 0 |
| C 6 -C 7 Alpha-olefins | 50.20 | 99.80 | 7.40 |
| C 8 -C 10 Alpha-olefins | 4.60 | 0 | 8.70 |
| Other substances | 0.90 | 0.18 | 0.21 |
Example 2
The deoxidation section of this example was the same as in example 1, and silica was used as the adsorbent packing, the packing type being pall rings. The total plate number of the adsorption and rectification tower is 90, 40 tower plates of the adsorption section, 23 tower plates of the rectification section and 26 tower plates of the stripping section. C4-C10 alkane and olefin raw materials enter at a 40 th tower plate (the middle part of an adsorption section), the operation pressure at the top of the tower is 1atm, the mass reflux ratio is 2.5, the temperature at the top of the tower is 45 ℃, and the temperature at the bottom of the tower is 200 ℃. One stream with the main composition of C6-C7 alkane and C4-C5 alkene is taken out from the side of the tray 14 and named as side stream 1, and the other stream with the main composition of C8-C10 alkane and C6-C7 alkene is taken out from the side of the tray 74 and named as side stream 2. The purity of each product after adsorptive rectification separation is shown in table 5. The purity of the alpha-olefin in the tower bottom C8-C10 reaches more than 99.7 wt.%, and the yield reaches 96%. And two streams of the side stream are directly fed into a rectification refining unit for further processing.
TABLE 6 physicochemical Properties of silicon oxide
TABLE 7 purity of the components of the respective streams after adsorptive rectification
The rectification refining unit adopts two rectifying towers to respectively process two material flows of a lateral line 1 and a lateral line 2, the material flow of the lateral line 1 enters a rectifying tower 5, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower A is 45, the operating pressure at the top of the tower is 1atm, the feeding position is the 20 th plate, and the mass reflux ratio is 1.5. The material flow in the lateral line 2 enters a rectifying tower 6, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower B is 55, the operating pressure is 1atm, the feeding position is the 30 th plate, and the mass reflux ratio is 2.3. After rectification and purification, the product stream component purities are shown in tables 6 and 7. The purity of the C4-C5 alpha-olefin product can reach 99.7 wt.%, the yield reaches 95%, the purity of the C6-C7 alpha-olefin product can reach 99.8 wt.%, and the yield reaches 93%.
TABLE 8 purity of the constituents of the various streams of the rectification column 5
| Raw material wt. -%) | Tower top wt. -%) | Column bottom wt. -%) | |
| C 4 -C 5 Alkane(s) | 0.11 | 0.08 | 0 |
| C 6 -C 7 Alkane(s) | 36.41 | 0.12 | 88.83 |
| C 8 -C 10 Alkane(s) | 0 | 0 | 0 |
| C 4 -C 5 Alpha-olefins | 62.41 | 99.70 | 8.85 |
| C 6 -C 7 Alpha-olefins | 0.17 | 0 | 0.49 |
| C 8 -C 10 Alpha-olefins | 0 | 0 | 0 |
| Other substances | 0.90 | 0.1 | 1.83 |
TABLE 9 purity of the constituents of the various streams of the rectification column 6
| Raw materials wt. -%) | Tower top wt. -%) | Column bottom wt. -%) | |
| C 4 -C 5 Alkane(s) | 0 | 0 | 0 |
| C 6 -C 7 Alkane(s) | 0.11 | 0.02 | 0 |
| C 8 -C 10 Alkane(s) | 44.21 | 0 | 83.79 |
| C 4 -C 5 Alpha-olefins | 0 | 0 | 0 |
| C 6 -C 7 Alpha-olefins | 50.21 | 99.81 | 7.41 |
| C 8 -C 10 Alpha-olefins | 4.58 | 0 | 8.70 |
| Other substances | 0.89 | 0.17 | 0.20 |
Example 3
The deoxidation section of this example is the same as that of example 1, the adsorbent packing is alumina, and the packing type is Raschig rings. The total plate number of the adsorption and rectification tower is 95, the adsorption section is 43 tower plates, the rectification section is 26 tower plates, and the stripping section is 30 tower plates. C4-C10 alkane and olefin raw materials enter a 43 th tower plate (the middle part of an adsorption section), the operation pressure at the top of the tower is 1atm, the mass reflux ratio is 2.6, the temperature at the top of the tower is 45 ℃, and the temperature at the bottom of the tower is 200 ℃. One stream with the main composition of C6-C7 alkane and C4-C5 alkene is taken out from the side of the tray 17 and named as side stream 1, and the other stream with the main composition of C8-C10 alkane and C6-C7 alkene is taken out from the side of the tray 76 and named as side stream 2. The purity of each product after adsorptive rectification separation is shown in table 8. The purity of the alpha-olefin in the tower bottom C8-C10 reaches more than 99.8 wt.%, and the yield reaches 95%. And two streams of the side stream are directly fed into a rectification refining unit for further processing.
TABLE 10 physicochemical Properties of silicon oxide
TABLE 11 purity of the components of the respective streams after adsorptive rectification
The rectification refining unit adopts two rectifying towers to respectively process two material flows of a lateral line 1 and a lateral line 2, the material flow of the lateral line 1 enters a rectifying tower 5, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower A is 45, the operating pressure at the top of the tower is 1atm, the feeding position is the 20 th plate, and the mass reflux ratio is 1.5. The material flow in the lateral line 2 enters a rectifying tower 6, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower B is 55, the operating pressure is 1atm, the feeding position is the 30 th plate, and the mass reflux ratio is 2.3. After rectification and purification, the product stream component purities are shown in tables 9 and 10. The purity of the C4-C5 alpha-olefin product can reach 99.5 wt.%, the yield reaches 94%, the purity of the C6-C7 alpha-olefin product can reach 99.6 wt.%, and the yield reaches 94%.
TABLE 12 purity of the constituents of the various streams of the rectification column 5
| Raw material wt. -%) | Tower top wt. -%) | Column bottom wt. -%) | |
| C 4 -C 5 Alkane(s) | 0.19 | 0.08 | 0 |
| C 6 -C 7 Alkane(s) | 36.23 | 0.22 | 88.93 |
| C 8 -C 10 Alkane(s) | 0 | 0 | 0 |
| C 4 -C 5 Alpha-olefins | 62.21 | 99.50 | 8.75 |
| C 6 -C 7 Alpha-olefins | 0.37 | 0 | 0.58 |
| C 8 -C 10 Alpha-olefins | 0 | 0 | 0 |
| |
1 | 0.2 | 1.74 |
TABLE 13 purity of the constituents of the various streams of the rectification column 6
| Raw material wt. -%) | Tower top wt. -%) | Column bottom wt. -%) | |
| C 4 -C 5 Alkane(s) | 0 | 0 | 0 |
| C 6 -C 7 Alkane(s) | 0.11 | 0.21 | 0 |
| C 8 -C 10 Alkane(s) | 44.41 | 0 | 84.01 |
| C 4 -C 5 Alpha-olefins | 0 | 0 | 0 |
| C 6 -C 7 Alpha-olefins | 50.11 | 99.61 | 7.38 |
| C 8 -C 10 Alpha-olefins | 4.48 | 0 | 8.41 |
| Other substances | 0.89 | 0.18 | 0.2 |
Example 4
The adsorption deoxidation process adopts the simulated moving bed in the example 1, and is formed by connecting 12 columns in series, wherein the columns are filled with deoxidation adsorbents, and the adsorbents are silica gel materials. And (3) feeding the light distillate oil of C4-C10 into a simulated moving bed for adsorption deoxidation, wherein the operation temperature is 100 ℃, the proportion of a desorbent to the raw material is 2.5, and the feeding and discharging positions are switched once every 360 seconds. After the simulated moving bed adsorption deoxidation, the extract and the raffinate respectively enter a rectifying tower for desorbent recycling. The extract tower is a packed tower, the packing is pall rings, the total number of the tower plates is 40, the feeding position is at the 20 th tower plate, the operating pressure is 1atm, and the mass reflux ratio is 1.1; the raffinate tower is also a packed tower, the total tower plate number is 80, the feeding position is the 40 th tower plate, the operating pressure is 1atm, and the mass reflux ratio is 2.2.
The compositions of the products separated by the adsorption and deoxidation process are shown in Table 11, the content of oxygen-containing compounds in the obtained C4-C10 alkane and alkene is less than 10 mu g/g, and the yield reaches 97 percent.
TABLE 14 purity of the components of each stream after adsorption deoxygenation
| C 4 -C 10 Alkane alkene | Oxygen-containing compound | |
| Raw material wt. -%) | 93.000 | 7.000 |
| Extract tower top wt. -%) | 28.500 | 71.500 |
| % by weight of the raffinate column vessel | 99.999 | 0.001 |
And C4-C10 alkane and olefin enter an adsorption rectifying tower after adsorption and deoxidation to be further separated, the adsorption rectifying tower is filled with adsorption filler to ensure that light and heavy components are fully separated, and the adsorption filler is of a pall ring type and adopts a Y molecular sieve. The total plate number of the adsorption and rectification tower is 95, the adsorption section comprises 45 tower plates, the rectification section comprises 20 tower plates, and the stripping section comprises 30 tower plates. C4-C10 alkane and olefin raw materials enter at the 45 th tower plate (the middle part of the adsorption section), the operation pressure at the top of the tower is 1atm, the mass reflux ratio is 3, the temperature at the top of the tower is 48 ℃, and the temperature at the bottom of the tower is 205 ℃. One stream with the main composition of C6-C7 alkane and C4-C5 alkene is taken out from the side of the tray 14 and named as side stream 1, and the other stream with the main composition of C8-C10 alkane and C6-C7 alkene is taken out from the side of the tray 80 and named as side stream 2. The purity of each product after adsorptive rectification separation is shown in table 12. The purity of the alpha-olefin in the tower bottom C8-C10 reaches 99.7 wt%, and the yield reaches 95%. And two streams of the side stream are directly fed into a rectification refining unit for further processing.
TABLE 15 physicochemical Properties of Y molecular sieves
The rectification refining unit adopts two rectifying towers to respectively process two material flows of a lateral line 1 and a lateral line 2, the material flow of the lateral line 1 enters a rectifying tower A, a packed tower is adopted, and the packing type is theta ring. The total number of plates of the rectifying tower A is 35, the operating pressure at the top of the tower is 1atm, the feeding position is the 15 th plate, and the mass reflux ratio is 1.7. The side stream 2 enters a rectifying tower B, a packed tower is adopted, and the packing type is theta ring. The total number of the plates of the rectifying tower B is 60, the operating pressure is 1atm, the feeding position is the 35 th plate, and the mass reflux ratio is 2.0. After rectification purification, the product stream component purities are shown in table 13 and table 14. The purity of the C4-C5 alpha-olefin product reaches 99.6 wt.%, and the yield reaches 92%; the purity of the C6-C7 alpha-olefin product reaches 99.6 wt%, and the yield reaches 93%.
TABLE 16 purity of the constituents of the respective streams after adsorptive rectification
TABLE 17 purity of the constituents of each stream of column A
TABLE 18 purity of the constituents of the various streams of the rectification column B
Claims (10)
1. A method for separating alpha-olefin by coupling Fischer-Tropsch light fraction oil adsorption distillation with olefin is characterized by comprising the following steps: the adsorption rectification tower comprises one or more adsorption rectification towers, and the packing inside the adsorption rectification tower is adsorption packing with olefin adsorption capacity; the adsorption filler is one or more of molecular sieve, modified molecular sieve, silicon oxide, modified silicon oxide, aluminum oxide and modified aluminum oxide; the operation temperature is 50-180 ℃ at the top of the tower, 100-200 ℃ at the bottom of the tower, 0.01-0.5MPa at the top of the operation pressure tower, and 5-80 theoretical plates, continuous or intermittent Fischer-Tropsch light fraction oil separation is carried out, saturated hydrocarbon products with low olefin content are obtained at the top of the tower, and high-purity alpha-olefin products are obtained at the bottom of the tower.
2. The method of claim 1 wherein the adsorbent packing is structured packing.
3. The method as claimed in claim 1, wherein the adsorption rectification column is an adsorption rectification column comprising a plurality of side draws, and products of different distillation stages are drawn.
4. The method of claim 1, wherein the adsorbent filler is one or more of a molecular sieve with acid centers, silica and alumina.
5. The method of claim 1, wherein the adsorptive filler is in NH 3 The acid center desorption temperature in the TPD analysis was 120-300 ℃.
6. The method as claimed in claim 3, wherein the products of different distillation sections obtained by the adsorption distillation tower enter an olefin refining unit, the olefin refining unit consists of a plurality of olefin refining distillation towers, an olefin product is obtained at the tower top, and an alkane product is obtained at the tower bottom.
7. The method according to claim 1, wherein the temperature at the top of the adsorption rectification column is 80-150 ℃, the temperature at the bottom of the adsorption rectification column is 180-200 ℃, the pressure at the top of the adsorption rectification column is 0.01-0.2 MPa, and the number of theoretical plates is 40-60.
8. The method of claim 1, wherein the alpha-olefin product purity is greater than or equal to 99% and the alpha-olefin yield is greater than or equal to 85%.
9. The method of claim 2, wherein the adsorptive filler is one or more of Raschig rings, theta rings, and pall ring fillers.
10. The method of claim 2 wherein the adsorbent packing is in NH 3 The desorption temperature of the acid center in TPD analysis is 200-250 ℃.
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| PCT/CN2023/106403 WO2023217303A1 (en) | 2022-05-09 | 2023-07-07 | Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin |
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| WO2023217303A1 (en) * | 2022-05-09 | 2023-11-16 | 中海油天津化工研究设计院有限公司 | Method for separating alpha-olefin from fischer-tropsch light distillate by using adsorption and distillation to couple olefin |
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| CN109652111A (en) * | 2019-01-16 | 2019-04-19 | 北京三聚环保新材料股份有限公司 | A kind of device and method separating alkene from Fischer-Tropsch synthesis oil |
| CN114395416A (en) * | 2021-12-17 | 2022-04-26 | 中海油天津化工研究设计院有限公司 | Method for producing polymer grade high carbon alpha-olefin by coal-based Fischer-Tropsch synthetic oil |
| CN115011376B (en) * | 2022-05-09 | 2023-12-12 | 中海油天津化工研究设计院有限公司 | Method for separating alpha-olefin by Fischer-Tropsch light distillate oil adsorption and rectification coupled olefin |
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