CN103539612B - Desulphurization method for propylene - Google Patents
Desulphurization method for propylene Download PDFInfo
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- CN103539612B CN103539612B CN201210239915.9A CN201210239915A CN103539612B CN 103539612 B CN103539612 B CN 103539612B CN 201210239915 A CN201210239915 A CN 201210239915A CN 103539612 B CN103539612 B CN 103539612B
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 51
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- 239000010457 zeolite Substances 0.000 claims abstract description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000003599 food sweetener Nutrition 0.000 claims abstract description 31
- 239000003765 sweetening agent Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 238000002447 crystallographic data Methods 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 7
- 230000023556 desulfurization Effects 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 29
- 230000008569 process Effects 0.000 abstract description 27
- 239000005864 Sulphur Substances 0.000 abstract description 22
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 21
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 238000010792 warming Methods 0.000 description 13
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229960003280 cupric chloride Drugs 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 hexamethylene imines Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BVJRIMBTLVPCFB-UHFFFAOYSA-N [Fe+2].[O-2].[Ca+2].[O-2] Chemical compound [Fe+2].[O-2].[Ca+2].[O-2] BVJRIMBTLVPCFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The present invention relates to a kind of Desulphurization method for propylene, mainly solve in prior art there is sweetening process complexity, Determination of Trace Sulfur is difficult to the problem that removes.The present invention is 0 ~ 100 DEG C by adopting in temperature of reaction, and in gauge pressure pressure for 0.2 ~ 2.0MPa, air speed is 0.1 ~ 10 hour
-1under condition, make propylene and desulfurization agent; Wherein, described sweetening agent comprises following component with weight parts: a) at least one zeolite being selected from ZSM-5, ZSM-12, β zeolite, MCM series zeolite, mordenite, faujusite or having in the zeolite of following XRD diffraction data of 10 ~ 90 parts; Described zeolite is through Cu
2+and Zn
2+modification, makes Na in zeolite
+content is less than 0.05 % by weight; B) technical scheme of the zinc oxide of 10 ~ 90 parts and the mixture of cupric oxide solves the problems referred to above preferably, can be used for removing in the industrial production of Trace Sulphur in Propene.
Description
Technical field
The present invention relates to a kind of Desulphurization method for propylene.
Background technology
Isopropyl benzene is important basic organic, is the important intermediate raw material producing phenol, acetone and alpha-methyl styrene.The traditional method of industrial production isopropyl benzene has the solid phosphoric acid method (SPA method) of UOP (UOP) and the improvement AlCl of Monsanto/Lummus Crest company
3method.But because catalytic erosion is strong, pollution is heavy and aftertreatment is numerous and diverse, be all eliminated at present.
Molecular sieve liquid phase alkylation methods due to reaction conditions relax, transformation efficiency is high, selectivity good, impurity is few, pollution-free, corrosion-free; Main By product polyisopropylbenzene can change isopropyl benzene into via reverse alkylation; make isopropyl benzene productive rate up to more than 99%; institute of Ge great industrial group company common concern in recent years, and an advanced technology of competitively development research, to significant " cleaning procedure " technology of environment protection.
The isopropyl benzene molecular sieve catalyst of heavy industrialization has Y zeolite, beta-molecular sieve and MCM molecular sieve at present.Above-mentioned sieve method all has strict demand to the sulphur content in raw material propylene.
Document CN93121638.9 provides a kind of copper zinc sweetening agent, can be used for the desulfurization of gas unsaturated hydrocarbons under hydro condition.CN90103718.4 provides a kind of liquid desulfuration method, adopts metal chelating and thing to process sulfur-bearing hydrocarbon-fraction under basic solution condition.CN01134688.4 provides a kind of method that iron calcium oxide removes mercaptan in industrial petroleum gas under alkali-free condition.CN86100015 provide a kind of with diatomite and silicon oxide, aluminum oxide for carrier, carry out composite modified hydro carbons liquid phase low-temp desulfurization agent with organic acid and mineral acid and tensio-active agent.CN1406914 provides the method for organosulfur in a kind of fluidized-bed ni based amorphous alloy Arene removal.The common drawback of all above-mentioned sweetening agents, sulfur method is poor to the sweetening effectiveness of Determination of Trace Sulfur, is difficult to make sulphur content to be reduced to content (being less than 30ppb) required by molecular sieve liquid phase synthesis isopropyl benzene technique.
Summary of the invention
Technical problem to be solved by this invention be there is sweetening process complexity in prior art, Determination of Trace Sulfur is difficult to the problem that removes, provides a kind of new Desulphurization method for propylene.The method have easy and simple to handle, sweetening effectiveness good, can remove the feature of Trace Sulphur in Propene, and the total sulfur content in raw material propylene can be made to be reduced to below 30ppb.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of Desulphurization method for propylene, is 0 ~ 100 DEG C in temperature of reaction, and in gauge pressure pressure for 0.2 ~ 2.0MPa, air speed is 0.1 ~ 10 hour
-1under condition, make propylene and desulfurization agent; Wherein, described sweetening agent comprises following component with weight parts:
A) at least one zeolite being selected from ZSM-5, ZSM-12, β zeolite, MCM series zeolite, mordenite, faujusite or having in the zeolite of following XRD diffraction data of 10 ~ 90 parts; Described zeolite is through Cu
2+and Zn
2+modification, makes Na in zeolite
+content is less than 0.05 % by weight;
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100） | |
| 6.5 0 | 28.8±0.1 | |
| 7.2 0 | 17.3±0.1 | |
| 8.8 0 | 15.4±0.1 | |
| 9.7 0 | 53.8±0.1 | |
| 13.5 0 | 39.4±0.1 | |
| 14 0 | 28.8±0.1 | |
| 14.3 0 | 19.2±0.1 | |
| 15.4 0 | 23.1±0.1 | |
| 19.5 0 | 34.6±0.1 | |
| 22.2 0 | 69.2±0.1 | |
| 23.8 0 | 23.1±0.1 | |
| 25.5 0 | 100±0.1 | |
| 26.2 0 | 65.4±0.1 | |
| 27.5 0 | 46.7±0.1 | |
| 31 0 | 27.9±0.1 | |
| 35.8 0 | 15.4±0.1 | ； |
B) zinc oxide of 10 ~ 90 parts and the mixture of cupric oxide, wherein the weight ratio of zinc oxide and cupric oxide is 1: (0.1 ~ 0.5).
In technique scheme, temperature of reaction preferable range is 0 ~ 55 DEG C, and in gauge pressure pressure preferable range for 0.5 ~ 1.5MPa, air speed preferable range is 0.3 ~ 2 hour
-1.Described zeolite preferred version is at least one being selected from MCM series zeolite or having in the zeolite of above-mentioned XRD diffraction data.MCM series zeolite preferred version is for being selected from MCM-22, MCM-49 or MCM-56.With weight parts, the consumption preferable range of zeolite is 40 ~ 65 parts, and the consumption preferable range of oxide compound is 35 ~ 60 parts.In zinc oxide and copper oxide mixture, the weight ratio preferable range of zinc oxide and cupric oxide is 1: (0.1 ~ 0.3).
Existing sweetening agent is of a great variety, but generally the sulphur in propylene can only be removed to ppm level, and the propylene used at a lot of commercial run to the requirement of sulphur content well below this value.The present inventor surprisingly finds in test: be selected from ZSM-5, ZSM-12, β zeolite, MCM series zeolite, mordenite, faujusite or at least one zeolite that has in the zeolite of specific XRD diffraction data shaping together with the mixture of zinc oxide, cupric oxide, under certain processing condition, the total sulfur content in propylene can be reduced to below 30ppb, there is good sweetening effectiveness.
Sweetening agent in the present invention can be prepared as follows:
A) at least one zeolite M zinc chloride being selected from ZSM-5, ZSM-12, β zeolite, MCM series zeolite, mordenite, faujusite or have in the zeolite of above-mentioned XRD diffraction data and cupric chloride mixing solutions are exchanged, make the content of sodium ion in molecular sieve in 0.05% (weight) below.Wherein, exchange temperature is 50 ~ 95 DEG C, and swap time is 1 ~ 15 hour, and liquid-solid volume ratio is 1 ~ 20, in zinc chloride and cupric chloride mixing solutions, and Zn
2+volumetric molar concentration be 0.2 ~ 0.5 mol/L, Cu
2+volumetric molar concentration be 0.2 ~ 0.5 mol/L.
B) the ZnCuM molecular sieve exchanged is mixed with cupric oxide, zinc oxide, add silicon sol solution roller forming, after drying, within 1 ~ 10 hour, obtain finished product sweetening agent 550 ~ 580 DEG C of roastings.
Sweetening agent is loaded in fixed-bed reactor, be forced into 2.0MPa with hot nitrogen, be warming up to 100 DEG C, after purging dehydration, be cooled to normal temperature.Then, passing into propylene feedstocks to be processed, is 0 ~ 100 DEG C in temperature of reaction, and in gauge pressure pressure for 0.2 ~ 2.0MPa, air speed is 0.1 ~ 10 hour
-1under condition, make propylene and desulfurization agent.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
1500 grams of water glass (modulus=2.8) and 500 grams of hexamethylene imines are mixed evenly, 50 grams of sodium aluminates and 25 grams of sodium hydroxide are mixed evenly in 500 grams of water.Above-mentioned two kinds of solution are mixed evenly under vigorous stirring, continue stirring 2 hours, add 500 grams of water and stir 1 hour.The above-mentioned solution mixed is formed jelly at 10 DEG C after aging 100 hours, for subsequent use.
25 grams of sodium aluminates and 20 grams of sodium hydroxide are dissolved in 500 grams of water and is mixed evenly, add 500 grams of (40% weight) silicon sol to stir, add 800 grams of pure water stirrings to be again mixed evenly, add the jelly 50 grams of above-mentioned preparation, continuing stirring proceeded in crystallizing kettle after 2 hours, stir crystallization 100 hours at 165 DEG C, filtration washing to pH=7 ~ 9,150 DEG C of oven dry.Gained sample called after M, its specific surface area is 520 meters
2/ gram, pore volume is 0.68 ml/g, and XRD diffraction data is as shown in table 1.
Table 1
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100） |
| 6.5 0 | 28.8 |
| 7.2 0 | 17.2 |
| 8.8 0 | 15.5 |
| 9.7 0 | 53.7 |
| 13.5 0 | 39.5 |
| 14 0 | 28.8 |
| 14.3 0 | 19.1 |
| 15.4 0 | 23.2 |
| 19.5 0 | 34.6 |
| 22.2 0 | 69.2 |
| 23.8 0 | 23.1 |
| 25.5 0 | 100 |
| 26.2 0 | 65.3 |
| 27.5 0 | 46.7 |
| 31 0 | 27.8 |
| 35.8 0 | 15.4 |
Get the molecular sieve M200 gram of above-mentioned synthesis, add 0.5 mol/L zinc chloride and 0.5 mol/L cupric chloride mixing solutions 500 milliliters, be warming up to 95 DEG C and exchange 2 hours, repeatedly exchange 6 times, the sodium ion in molecular sieve is 0.035 % by weight.Molecular sieve M150 good for above-mentioned exchange gram is mixed evenly with 75 grams of zinc oxide, 75 grams of cupric oxide, uses silicon sol roller forming.By the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and within 4 hours, obtain finished product propylene sweetening agent T1.
Get 50 grams of propylene sweetening agent T1, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 25 DEG C, reaction pressure 1.0MPa, pending fresh propylene was with liquid mass air speed WHSV 1.5 hours
-1, continuously process 1000 hours, sweetening agent T1 performance does not decline, and obtains 75 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 1ppm, and after process, outlet detects sulphur content is 14ppb.
[embodiment 2]
Get 50 grams of propylene sweetening agent T1, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 5 DEG C, reaction pressure 0.7MPa, pending fresh propylene was with liquid mass air speed WHSV 0.5 hour
-1, continuously process 1000 hours, sweetening agent T1 performance does not decline, and obtains 25 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 0.9ppm, and after process, outlet detects sulphur content is 15ppb.
[embodiment 3]
Get 50 grams of propylene sweetening agent T1, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 55 DEG C, reaction pressure 1.5MPa, pending fresh propylene was with liquid mass air speed WHSV 2.0 hours
-1, process 1000 hours continuously, sweetening agent T1 performance does not decline, and obtains the propylene that double centner is qualified.Before process, in propylene, sulphur content is detected as 1.1ppm, and after process, outlet detects sulphur content is 21ppb.
[embodiment 4]
Get 200 grams, MCM-22 molecular sieve, add 0.5 mol/L zinc chloride and 0.5 mol/L cupric chloride mixing solutions 500 milliliters, be warming up to 95 DEG C and exchange 2 hours, repeatedly exchange 6 times, the sodium ion in molecular sieve is 0.038 % by weight.Molecular sieve M150 good for above-mentioned exchange gram is mixed evenly with 75 grams of zinc oxide, 15 grams of cupric oxide, uses silicon sol roller forming.By the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and within 4 hours, obtain finished product propylene sweetening agent T2.
Get 50 grams of propylene sweetening agent T2, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 25 DEG C, reaction pressure 1.0MPa, pending fresh propylene was with liquid mass air speed WHSV 1.0 hours
-1, continuously process 1000 hours, sweetening agent T2 performance does not decline, and obtains 50 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 1ppm, and after process, outlet detects sulphur content is 30ppb.
[embodiment 5]
Get ZSM-5 molecular sieve 200 grams, add 0.5 mol/L zinc chloride and 0.5 mol/L cupric chloride mixing solutions 500 milliliters, be warming up to 95 DEG C and exchange 2 hours, repeatedly exchange 6 times, the sodium ion in molecular sieve is 0.020 % by weight.Molecular sieve M150 good for above-mentioned exchange gram is mixed evenly with 75 grams of zinc oxide, 15 grams of cupric oxide, uses silicon sol roller forming.By the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and within 4 hours, obtain finished product propylene sweetening agent T3.
Get 50 grams of propylene sweetening agent T3, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 25 DEG C, reaction pressure 1.0MPa, pending fresh propylene was with liquid mass air speed WHSV 0.8 hour
-1, continuously process 1000 hours, sweetening agent T3 performance does not decline, and obtains 40 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 1ppm, and after process, outlet detects sulphur content is 28ppb.
[embodiment 6]
Get mordenite 200 grams, add 0.5 mol/L zinc chloride and 0.5 mol/L cupric chloride mixing solutions 500 milliliters, be warming up to 95 DEG C and exchange 2 hours, repeatedly exchange 6 times, the sodium ion in molecular sieve is 0.030 % by weight.Molecular sieve M150 good for above-mentioned exchange gram is mixed evenly with 75 grams of zinc oxide, 15 grams of cupric oxide, uses silicon sol roller forming.By the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and within 4 hours, obtain finished product propylene sweetening agent T4.
Get 50 grams of propylene sweetening agent T4, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 30 DEG C, reaction pressure 1.0MPa, pending fresh propylene was with liquid mass air speed WHSV 1.0 hours
-1, continuously process 1000 hours, sweetening agent T4 performance does not decline, and obtains 50 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 1ppm, and after process, outlet detects sulphur content is 27ppb.
[embodiment 7]
Get 200 grams, β zeolite, add 0.5 mol/L zinc chloride and 0.5 mol/L cupric chloride mixing solutions 500 milliliters, be warming up to 95 DEG C and exchange 2 hours, repeatedly exchange 6 times, the sodium ion in molecular sieve is 0.030 % by weight.Molecular sieve M150 good for above-mentioned exchange gram is mixed evenly with 75 grams of zinc oxide, 15 grams of cupric oxide, uses silicon sol roller forming.By the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and within 4 hours, obtain finished product propylene sweetening agent T5.
Get 50 grams of propylene sweetening agent T5, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 30 DEG C, reaction pressure 1.0MPa, pending fresh propylene was with liquid mass air speed WHSV 1.0 hours
-1, continuously process 1000 hours, sweetening agent T5 performance does not decline, and obtains 50 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 1ppm, and after process, outlet detects sulphur content is 29ppb.
[embodiment 8]
Get Y zeolite 200 grams, add 0.5 mol/L zinc chloride and 0.5 mol/L cupric chloride mixing solutions 500 milliliters, be warming up to 95 DEG C and exchange 2 hours, repeatedly exchange 6 times, the sodium ion in molecular sieve is 0.038 % by weight.Molecular sieve M150 good for above-mentioned exchange gram is mixed evenly with 75 grams of zinc oxide, 15 grams of cupric oxide, uses silicon sol roller forming.By the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and within 4 hours, obtain finished product propylene sweetening agent T6.
Get 50 grams of propylene sweetening agent T6, be positioned in fixed-bed reactor, under ensureing that system for handling is liquid phase and temperature of reaction 30 DEG C, reaction pressure 1.0MPa, pending fresh propylene was with liquid mass air speed WHSV 1.0 hours
-1, continuously process 1000 hours, sweetening agent T6 performance does not decline, and obtains 50 kilograms of qualified propylene.Before process, in propylene, sulphur content is detected as 1ppm, and after process, outlet detects sulphur content is 28ppb.
Claims (5)
1. a Desulphurization method for propylene is 0 ~ 100 DEG C in temperature of reaction, and in gauge pressure pressure for 0.2 ~ 2.0MPa, air speed is under 0.1 ~ 10 hour-1 condition, makes propylene and desulfurization agent; Wherein, described sweetening agent comprises following component with weight parts:
A) at least one zeolite being selected from ZSM-5, ZSM-12, β zeolite, MCM series zeolite, mordenite, faujusite or having in the zeolite of following XRD diffraction data of 10 ~ 90 parts; Described zeolite is through Cu
2+and Zn
2+modification, makes Na in zeolite
+content is less than 0.05 % by weight;
；
B) zinc oxide of 10 ~ 90 parts and the mixture of cupric oxide, wherein the weight ratio of zinc oxide and cupric oxide is 1: (0.1 ~ 0.5).
2. Desulphurization method for propylene according to claim 1, is characterized in that temperature of reaction is 0 ~ 55 DEG C, and in gauge pressure pressure for 0.5 ~ 1.5MPa, air speed is 0.3 ~ 2 hour
-1.
3. Desulphurization method for propylene according to claim 1, is characterized in that described zeolite is selected from MCM series zeolite or has at least one in the zeolite of above-mentioned XRD diffraction data.
4. Desulphurization method for propylene according to claim 1, is characterized in that MCM series zeolite is selected from MCM-22, MCM-49 or MCM-56.
5. Desulphurization method for propylene according to claim 1, is characterized in that the weight ratio of zinc oxide and cupric oxide is 1: (0.1 ~ 0.3).
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