CN1267535C - Light hydrocarbon dearsenicating agent and its preparing method - Google Patents
Light hydrocarbon dearsenicating agent and its preparing method Download PDFInfo
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- CN1267535C CN1267535C CN 200310102237 CN200310102237A CN1267535C CN 1267535 C CN1267535 C CN 1267535C CN 200310102237 CN200310102237 CN 200310102237 CN 200310102237 A CN200310102237 A CN 200310102237A CN 1267535 C CN1267535 C CN 1267535C
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- dearsenification
- silver
- agent
- dearsenic
- dearsenic agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229940100890 silver compound Drugs 0.000 claims abstract description 11
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 7
- 230000023556 desulfurization Effects 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 35
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 34
- 235000003599 food sweetener Nutrition 0.000 claims description 19
- 239000003765 sweetening agent Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 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 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Chemical group 0.000 claims 1
- 239000011593 sulfur Chemical group 0.000 claims 1
- 150000002506 iron compounds Chemical class 0.000 abstract description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract 4
- 230000003009 desulfurizing effect Effects 0.000 abstract 3
- 229910001923 silver oxide Inorganic materials 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 5
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 methyl hydrogen arsenide Chemical compound 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 241001311547 Patina Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- IPZRPYCWPXDPEX-UHFFFAOYSA-N [As].[Ag].[Ag].[Ag] Chemical compound [As].[Ag].[Ag].[Ag] IPZRPYCWPXDPEX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical group C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a gas or liquid light hydrocarbon dearsenic agent or a dearsenic desulfurizing agent and application in cracked gas or liquid C<1 to 8> hydrocarbon dearsenic or dearsenic desulfurization. The dearsenic agent is composed of silver and a carrier, and the silver is in at least one form of silver oxide (I), silver oxide (II), ion state silver, metallic state silver or combination thereof. The dearsenic desulfurizing agent is composed of silver compounds, iron compounds and a carrier, iron accounts for 0.05 to 20 wt% according to the total weight of the dearsenic desulfurizing agent, and the weight ratio of the silver to the iron is 0.1: 1 to 1: 1.
Description
Technical field
The present invention relates to a kind of hydrocarbon dearsenicating catalyst and/or dearsenification sweetening agent and application thereof.More particularly, the present invention relates to the dearsenification sweetening agent formed by silver compound and carrier or silver compound and iron cpd and carrier and at hydrocarbon gas and liquid C
1-8Application in hydrocarbon dearsenicating or the dearsenification desulfurization.
Background technology
As everyone knows, in most of crude oil and shale oil, there is the arsenic of various forms, for example hydrogen arsenide, methyl hydrogen arsenide, ethyl hydrogen arsenide, arsenous methide, arsenous ethide and arsenic triphenyl etc.When handling this class oil product with cracking, fractionation or additive method and separate, these arsenides just enter respectively in the product fraction by the height of its boiling point.When these petroleum cuts processes are further handled, particularly comprise when the catalyzer of forming with precious metal is further handled, because arsenic can make the noble metal catalyst poisoning, thereby extremely harmful.At present, various dearsenic agents and arsenic removing method are disclosed both at home and abroad.For example, CN 86101838 A have disclosed CuO/ZnO/Al
2O
3Dearsenic agent, this dearsenic agent can remove C
2And C
3Deng the arsenide in hydro carbons and the rare gas element, but for the removing of arsenic in the splitting gas that contains a large amount of hydrogen, dearsenification efficient is not high.Simultaneously, the alkynes that contains in the material might generate acetylenic ketone through dearsenic agent.On the other hand, the preparation method of this dearsenic agent is complicated.
US 6383981 has disclosed Fe
2O
3/ MnO
2/ Al
2O
3Dearsenic agent, higher to the arsenic removal efficiency in alkene or the alkane, still, this dearsenic agent is low to the arsenic removal efficiency in the splitting gas fraction.
US 4996030 has described CuO/MnO
2/ Al
2O
3Dearsenic agent, this dearsenic agent is not suitable for the dearsenification of splitting gas fraction yet.
The NiO/Al that CN 1030440A and US 4849577 propose
2O
3And NiO/PbO/Al
2O
3In the dearsenic agent, the NiO of oxidation state does not almost have the dearsenification activity.In 300～450 ℃ of hydrogen environments after the prereduction, though certain dearsenification activity is arranged, the Ni that goes back ortho states makes the hydrogenation of unsaturated hydrocarbons in the splitting gas fraction, has changed the composition of material, and dearsenification effect instability.
EP 0865814 A2 and the disclosed AgO/MnO of JP 11-19475A
2And Ag
2The O/CuO dearsenic agent has adopted that arsenic is had the silver compound that efficiently removes ability is active ingredient, but the carrier of these dearsenic agents is manganese oxide or cupric oxide, complicated process of preparation, and cost is higher, and these dearsenic agents only are applicable to removing of arsenic in the semi-conductor industry waste gas.
It is reported that the MEP191 dearsenic agent that French Inst Francais Du Petrole produces is an active ingredient with PbO, the arsenic of 50～100ppb in the material can be removed to less than 5ppb, still, material arsenic content reached under the situation of 1000～2000ppb that the dearsenification degree of depth of this dearsenic agent is report not.
The dearsenic agent that JP154610A introduces, its active ingredient is the patina thing, mainly is at the dearsenification of gas or hydrocarbon-containiproducts gas, does not relate to the dearsenification to the liquid phase hydro carbons, the preparation technology of its dearsenic agent is more complicated also.Simultaneously, dearsenification and desulfurization are separately carried out, the flow process complexity.
As mentioned above, dearsenic agent of the prior art is an active ingredient with Cu, Zn, Pb, Fe, Co, Ni, Mn, Ag etc., with aluminum oxide, titanium dioxide, silicon oxide, molecular sieve, diatomite, gac, silico-aluminate or clay etc. is carrier, on carrier, the dearsenic agent that obtains has certain effect of removing arsenic to some material with active constituent loading.But, do not point out the liquid towards light hydrocarbon to have the desulphurizing activated dearsenification sweetening agent of high dearsenification.The inventor has carried out research for a long time and in depth to the dearsenification activity of the different shape of silver compound, discovery is carried the silver compound of different shape and is held on the carrier, obtained that splitting gas and liquid light hydrocarbon fraction are all had the desulphurizing activated dearsenification sweetening agent of high dearsenification, the preparation technology of this dearsenic agent is simple simultaneously, sulphur and arsenic are had the dearsenification sweetening agent of removal effect simultaneously, thereby finished the present invention.
Summary of the invention
The purpose of this invention is to provide a kind of dearsenic agent that constitutes by patina thing and carrier.
Another object of the present invention provides the preparation method of described dearsenic agent
The 3rd purpose of the present invention provides the arsenic removing method of splitting gas and liquid light hydrocarbon.
The 4th purpose of the present invention provides dearsenification sweetening agent of light hydrocarbons and preparation method thereof, and wherein the decreasing ratio of arsenic is more than 95%, and the decreasing ratio of sulphur is 50%.
Dearsenic agent of the present invention is made up of silver compound and carrier.Described silver compound on carrier with the silver of the silver of silver suboxide (I), silver suboxide (II), ionic state, metallic state or at least a existence in its combination.The silver of various forms can both remove arsenide effectively, and the silver compound of different shape can transform under certain condition mutually.
Silver Nitrate and hydrogen arsenide reaction generate silver arsenide and arsenus acid, and reaction formula is:
Silver suboxide and hydrogen arsenide reaction can generate arsenic powder and silver, and reaction formula is:
Prepare in the present invention that employed silver-colored source is a silver suboxide in the dearsenic agent; Silver halide such as silver chloride, Silver monobromide or Silver iodide etc.; Oxysalt such as the Silver Nitrate or the silver carbonate etc. of silver; Organic acid salt such as the silver acetate or the silver oxalate etc. of silver.
Employed in the present invention carrier can use a kind of in the group that aluminum oxide, molecular sieve, silicon oxide, diatomite or gac form.The preferred aluminum oxide that uses more preferably uses γ type aluminum oxide.The specific surface area of carrier is generally 50-400 rice
2/ gram is preferably 100-300 rice
2/ gram, pore volume is 0.3-1.8 milliliter/gram, is preferably 0.4-1.5 milliliter/gram.
Dearsenic agent of the present invention, in the gross weight (weight of carrier+active ingredient) of dearsenic agent, silver is 0.05%～20 weight %, is preferably 0.1%～10 weight %.
Dearsenification sweetening agent of the present invention is characterized in that being made up of silver compound and iron cpd and carrier
Described dearsenification sweetening agent, in the gross weight of dearsenification sweetening agent, iron is 0.05～20 weight %, silver is 0.1 with the weight ratio of iron: 1-1: 1.
The preparation method of dearsenic agent of the present invention or dearsenification sweetening agent has no particular limits, and is held in carrier surface as long as active ingredient patina thing and/or iron compound high dispersing ground are carried.For example, can adopt preparation dearsenic agent of the present invention or dearsenification desulfurization such as pickling process, spraying method or kneading method.Adopt the dearsenic agent or the dearsenification sweetening agent of straight dipping process, neutralisation and decomposition method preparation all to have good performance.Preparation method of the present invention has no particular limits, and preparation technology is simple, has saved production cost, has improved economic benefit.
The method that removes arsenic and/or sulphur from gaseous state or liquid light hydrocarbons of the present invention is to make splitting gas or the C that contains arsenic and/or sulphur
1-8The liquefied hydrocarbon material contacts with dearsenic agent of the present invention or dearsenification sweetening agent.Arsenic content in the charging is below the 2000ppb, and sulphur content is 0.1～50ppm, and the gaseous feed air speed is 2000～15000h
-1, the liquid feed air speed is 2～20h
-1The working temperature that material contacts with dearsenic agent is envrionment temperature～100 ℃, and operating pressure is 0.2～4.0Mpa.
Dearsenic agent of the present invention reaches after the constant volume the absorption of arsenic, can regenerate, and adopts bubbling air regeneration during regeneration, and temperature is 100～300 ℃, and the dearsenification performance of regeneration back dearsenic agent is restored, and has increased the work-ing life of dearsenic agent like this.
Embodiment
Below, further describe the present invention by embodiment, still, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in appended claims book subsequently.
Embodiment 1
The preparation of dearsenic agent
To add 3 weight % Silver Nitrates preparation steeping fluid, with " dry impregnation method " preparation with the spherical alumina carrier of 100 grams that takes off method production soon.Making the weight percentage of silver in the dearsenic agent is 2.5%, and impregnated dearsenic agent is standby after 110～120 ℃ of dry a few hours.The form of silver is the silver of ionic state in the dearsenic agent of this kind method preparation.This dearsenic agent particle diameter is φ 2.0～3.5mm, and test adopts fixed bed to carry out, and reactor is φ 14 * 2 * 480 stainless steel tubes, and dearsenic agent is cut into 1/2～1/4 size of former grain, loadings 2.0ml.Test raw material is the splitting gas of ethylene unit, manually allocates hydrogen arsenide into.
The splitting gas that will contain about arsenic 1000ppb passes through above-mentioned dearsenic agent, and arsenic content is lower than 10ppb in the discharging of handling.
Operating result is listed in the table 1.
Table 1
| Time h | Temperature ℃ | Pressure MPa | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | ||||
| 16 | 40 | 0.6 | 10000 | 811 | 5.1 |
| 22 | 40 | 0.6 | 10000 | 811 | 5.1 |
| 46 | 40 | 0.6 | 10000 | 811 | 3.4 |
| 70 | 40 | 0.6 | 10000 | 811 | ＜1 |
| 76 | 40 | 0.6 | 10000 | 811 | ＜1 |
| 100 | 40 | 0.6 | 10000 | 811 | 1.6 |
| 118 | 40 | 0.6 | 10000 | 811 | ＜1 |
| 124 | 40 | 0.6 | 15000 | 811 | 2.6 |
| 142 | 40 | 0.6 | 15000 | 861 | 1.7 |
| 148 | 40 | 0.3 | 15000 | 861 | 1.6 |
| 172 | 40 | 0.2 | 15000 | 861 | 1.5 |
In addition, this dearsenic agent is used to contain C
4And C
5The dearsenification of liquid propylene, effect is also fine, test-results is as shown in table 2.
Table 2
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 16 | 40 | 20 | 1165 | 4.1 |
| 64 | 40 | 20 | 1165 | ＜1 |
| 118 | 40 | 20 | 2138 | ＜1 |
| 142 | 40 | 20 | 2138 | 4.0 |
| 166 | 40 | 20 | 2138 | ＜1 |
| 198 | 40 | 20 | 2014 | ＜1 |
| 222 | 40 | 20 | 2014 | ＜1 |
| 270 | 40 | 20 | 2014 | ＜1 |
Embodiment 2
In this example, the dearsenic agent for preparing among the embodiment 1 is neutralized with sodium hydroxide solution, after question response is complete, with water wash for several times, with flush away Na
+And NO
3 -, dry then.Test raw material is for joining the arsenic splitting gas.The form of silver is the silver of oxidation state in this catalyzer.
The results are shown in Table 3 in the dearsenification of above-mentioned dearsenic agent.
Table 3
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 47 | 40 | 2000 | 606 | 6.2 |
| 99 | 40 | 2000 | 606 | 7.7 |
| 271 | 40 | 2000 | 730 | 9.7 |
| 295 | 40 | 2000 | 730 | 1.7 |
| 391 | 40 | 2000 | 730 | 6.7 |
| 439 | 40 | 2000 | 780 | 5.0 |
| 463 | 40 | 2000 | 780 | 1.7 |
| 535 | 40 | 2000 | 780 | 6.2 |
| 559 | 40 | 2000 | 780 | ＜1 |
| 610 | 40 | 2000 | 1063 | ＜1 |
| 634 | 40 | 2000 | 1063 | ＜1 |
(continuing) table 3
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 658 | 40 | 2000 | 1063 | 1.5 |
| 684 | 40 | 4000 | 1055 | 10.5 |
| 718 | 40 | 4000 | 1055 | 6.0 |
| 798 | 40 | 4000 | 1055 | 1.4 |
| 822 | 40 | 4000 | 1055 | ＜1 |
| 870 | 40 | 4000 | 1055 | ＜1 |
| 894 | 40 | 8000 | 937 | 2.9 |
| 918 | 40 | 8000 | 937 | ＜1 |
| 942 | 40 | 8000 | 937 | 9.4 |
| 1024 | 40 | 10000 | 892 | ＜1 |
| 1042 | 40 | 10000 | 892 | ＜1 |
Embodiment 3
In this example, the dearsenic agent with preparation in the example 1 decomposed 4 hours in 450 ℃ in air.Test raw material is also for joining the arsenic splitting gas.The form of silver is a simple substance silver in this dearsenic agent.
The results are shown in Table 4 in the dearsenification of above-mentioned dearsenic agent.
Embodiment 4
In this example, with 2.0 gram AgNO
3Be dissolved in 14 ml waters, take by weighing 20 gram Al
2O
3Ball immerses in the above-mentioned solution, and under 110 ℃ condition dry 2 hours, take by weighing 3.3 gram FeSO in addition
4.7H
2O is dissolved in 14 ml waters, immerse above-mentioned dearsenic agent, in 90 ℃ of dryings 2 hours, above-mentioned product is dissolved in 12 milliliters of NaOH solution at last, wherein contain 3.0 gram NaOH, in 90 ℃ of dryings 2 hours, the activation 2 hours in 350 ℃ of nitrogen atmosphere of dry back, obtain the dearsenification desulfurization catalyst, its dearsenification desulfurization performance is as shown in table 5:
Table 4
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 16 | 40 | 10000 | 810.6 | 4.9 |
| 22 | 40 | 10000 | 810.6 | 5.1 |
| 46 | 40 | 10000 | 810.6 | 5.0 |
| 70 | 40 | 10000 | 810.6 | 3.3 |
| 76 | 40 | 10000 | 810.6 | ＜1 |
| 100 | 40 | 10000 | 810.6 | 5.0 |
| 118 | 40 | 10000 | 810.6 | ＜1 |
| 124 | 40 | 15000 | 810.6 | ＜1 |
| 142 | 40 | 15000 | 861 | 1.7 |
| 148 | 40 | 15000 | 861 | 1.6 |
| 172 | 40 | 15000 | 861 | ＜1 |
The data of table 1～4 show that the money base dearsenic agent has been removed the arsenic compound in splitting gas and the liquid light hydrocarbons basically.
Table 5
| Temperature ℃ | Air speed h -1 | Arsenic content ppb | Sulphur content ppm | ||
| Charging | Discharging | Charging | Discharging | ||
| 40 | 5000 | 5244 | 60.86 | 6.6 | 3.2 |
| 40 | 3000 | 5244 | 31.61 | 6.2 | 3.8 |
| 40 | 3000 | 5244 | 35.88 | 7.0 | 2.4 |
Table 5 shows: dearsenification sweetening agent of the present invention can remove arsenide and the most sulfide in the hydro carbons.
Comparative example 1
With cupric nitrate, zinc nitrate and aluminum nitrate obtain solution by a certain percentage, be precipitation agent with yellow soda ash, make the oxyhydroxide co-precipitation of these metals.Throw out through washing, dry after roasting in air, make the oxyhydroxide of co-precipitation generate corresponding oxide compound, compression molding then, the percentage composition in the finished product dearsenic agent is CuO=35%～40%, ZnO=15%～25%, Al
2O
3Be surplus.
The dearsenic agent of above-mentioned preparation is cut into 1/4～1/8 particle, adopts the test conditions identical with embodiment 1 to examine this dearsenic agent, dearsenification the results are shown in Table 6.
Comparative example 2
Adopt immersion process for preparing CuO/Al
2O
3Dearsenic agent, CuO weight content are 16%, also adopt with embodiment 1 identical condition and carry out the dearsenification test, the results are shown in Table 6.
Table 6
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | ||
| Charging | Discharging I | Discharging II | |||
| 4 | 40 | 10000 | 1441 | ＜1 | ＜1 |
| 22 | 40 | 10000 | 1441 | 23.4 | 82.2 |
| 28 | 40 | 10000 | 1441 | 29.5 | 108.1 |
| 46 | 40 | 10000 | 1441 | 179.5 | 238.7 |
| 70 | 40 | 10000 | 1441 | 321.2 | 487.2 |
Annotate: discharging I is the discharging of comparative example 1
Discharging II is the discharging of comparative example 2
Comparative example 3
The method of introducing according to US 6383981 prepares Fe
2O
3/ MnO
2/ Al
2O
3Dearsenic agent adopts the condition identical with embodiment 1 to test, and the results are shown in Table 7.
Comparative example 4
The method of introducing according to US 4996030 prepares CuO/MnO
2/ Al
2O
3Dearsenic agent adopts the condition identical with embodiment 1 to test, and the results are shown in Table 7.
Table 7
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | ||
| Charging | Discharging I | Discharging II | |||
| 16 | 40 | 10000 | 1441 | 789 | 229 |
| 22 | 40 | 10000 | 1441 | 888 | 279 |
| 28 | 40 | 5000 | 1441 | 654 | 117.3 |
| 50 | 40 | 5000 | 1441 | 835 | 193.4 |
Annotate: discharging I is the discharging of comparative example 3
Discharging II is the discharging of comparative example 4
Comparative example 5
The method of introducing according to CN 1030440A prepares NiO/Al
2O
3Dearsenic agent, the oxidation state NiO of nickel does not have the dearsenification activity in this dearsenic agent, carries out twice reduction afterwards in hydrogen atmosphere, and reductive condition is: pressure 0.2MPa, H
2Air speed 1500h
-1, reduction temperature is incubated 4 hours down, and reduction temperature is 200 ℃ for the first time, and the dearsenic agent activity does not almost improve, and reduction temperature is 400～450 ℃ for the second time, and initially the dearsenification activity is very high, but descends soon, and dearsenification the results are shown in Table 8.
Table 8
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 16 | 40 | 10000 | 1441 | 1444 |
| 48 | 40 | 5000 | 1661 | 1306 |
| 72 | 40 | 5000 | 1661 | ＜1 |
| 96 | 40 | 5000 | 1661 | 92.1 |
| 122 | 40 | 5000 | 1661 | 476 |
Annotate: carry out the reduction first time after 16 hours, carry out the reduction second time after 48 hours.
Comparative example 6
By the method that the patent US4849577 of Inst Francais Du Petrole introduces, be that steeping fluid prepares PbO/Al with the plumbic acetate
2O
3Dearsenic agent, PbO content are 17%, adopt the condition identical with example one to carry out evaluation test, the results are shown in Table 9.
Table 9
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 3 | 40 | 10000 | 892 | 3.65 |
| 21 | 40 | 10000 | 892 | 105.3 |
| 27 | 40 | 10000 | 892 | 142.8 |
Comparative example 7
With the lead nitrate solution is steeping fluid, is carrier with spherical aluminium sesquioxide, adopts " dry impregnation method " preparation PbO/Al
2O
3Dearsenic agent, PbO weight percentage are 20%, adopt the condition identical with embodiment 1 to test, and the results are shown in Table 10.
Table 10
| Time h | Temperature ℃ | Air speed h -1 | Arsenic content ppb | |
| Charging | Discharging | |||
| 16 | 40 | 10000 | 1441 | 425 |
| 24 | 40 | 10000 | 1441 | 463 |
| 30 | 40 | 10000 | 1661 | 595 |
| 48 | 40 | 5000 | 1661 | 359 |
| 72 | 40 | 5000 | 1661 | 591 |
| 96 | 40 | 5000 | 1661 | 621 |
| 122 | 40 | 5000 | 1661 | 847 |
Claims (5)
1.. a dearsenification sweetening agent is characterized in that being made up of silver compound and iron cpd and carrier, in the gross weight of dearsenification sweetening agent, silver is 0.05%～20 weight %, and iron is 0.05-20 weight %, and silver is 0.1 with the weight ratio of iron: 1-1: 1.
2. by the described dearsenification sweetening agent of claim 1, it is characterized in that described carrier is selected from a kind of in the group of being made up of aluminum oxide, molecular sieve, silicon oxide, diatomite or gac.
3. any dearsenification sweetening agent application in dearsenification desulfurization from gaseous state or liquefied hydrocarbon of claim 1-2 record is to make gaseous state or the liquid C that contains arsenic and sulfur-bearing
1-8Hydro carbons contacts with any dearsenification sweetening agent of claim 1-2 record.
4. application according to claim 3, the working temperature that hydrocarbon contacts with dearsenic agent or dearsenification sweetening agent are envrionment temperature～100 ℃, and operating pressure is 0.2～4.0MPa, and the liquid feed air speed is 2～20h
-1, the gaseous feed air speed is 2000～15000h
-1
5. according to the application of claim 3 or 4, it is characterized in that sulfide content is 0.1～50ppm in the charging.
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|---|---|---|---|
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|---|---|---|---|
| CN 200310102237 CN1267535C (en) | 2003-10-29 | 2003-10-29 | Light hydrocarbon dearsenicating agent and its preparing method |
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| Publication Number | Publication Date |
|---|---|
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| CN1267535C true CN1267535C (en) | 2006-08-02 |
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|---|---|---|---|
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| CN102973658B (en) * | 2012-12-17 | 2016-03-23 | 伊春金北药制药有限公司 | Sugarless type cough-relieving Qinbaohong mixture and method for making thereof |
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|---|---|---|---|---|
| CN104624223B (en) * | 2015-02-09 | 2018-01-26 | 北京北大先锋科技有限公司 | A kind of continuous dearsenic catalyst for industrial tail gas purification and preparation method thereof |
| CN113999085B (en) * | 2021-12-02 | 2023-12-22 | 西安元创化工科技股份有限公司 | Deep purification method of hydrocarbon raw material |
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Cited By (1)
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| CN102973658B (en) * | 2012-12-17 | 2016-03-23 | 伊春金北药制药有限公司 | Sugarless type cough-relieving Qinbaohong mixture and method for making thereof |
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