CN106179328B - A kind of deep purifying desulfurizing agent and preparation method thereof - Google Patents
A kind of deep purifying desulfurizing agent and preparation method thereof Download PDFInfo
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- CN106179328B CN106179328B CN201610536607.0A CN201610536607A CN106179328B CN 106179328 B CN106179328 B CN 106179328B CN 201610536607 A CN201610536607 A CN 201610536607A CN 106179328 B CN106179328 B CN 106179328B
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 229910001676 gahnite Inorganic materials 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000003245 coal Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 239000010742 number 1 fuel oil Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000007602 hot air drying Methods 0.000 claims description 3
- HOOANQZZUGPTRH-UHFFFAOYSA-N molybdenum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mo+3].[Mo+3] HOOANQZZUGPTRH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 15
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses a kind of deep purifying desulfurizing agents and preparation method thereof.The deep purifying desulfurizing agent is by ZnAl2O4, metal oxide and alkali metal hydroxide or carbonate composition, ZnAl by weight percentage in deep purifying desulfurizing agent finished product2O4Account for that 60~90%, metal oxide accounts for 8~30%, alkali metal hydroxide or carbonate accounts for 2~15%.Deep purifying desulfurizing agent provided by the invention can be by COS and H in low-temp methanol washing process exiting syngas2S is further removed to equal < 5ppb, the catalyst such as protection downstream methanol synthesis, methanation, F- T synthesis, DMO synthesis.
Description
Technical field:
The present invention relates to removing COS and H2The technical field of S, more particularly in coal oil, natural gas from coal (SNG), big
Low-temp methanol washing process outlet COS and H is further removed in the devices such as type ammonia from coal, coal-ethylene glycol2The deep purifying essence of S
Desulfurizing agent.
Background technique:
Currently, more than 270 families of Chinese methanol enterprise, production capacity is more than 50,000,000 tons, accounts for the 46.8% of world's production capacity.Thus may be used
See, average every enterprise's methanol production capacity is less than 200,000 tons.2006-2008 methanol prices, which sharp rise, leads to a large amount of methanol projects
Start, from 2009, due to the influence of world financial crisis, methanol prices were sluggish, and production capacity is extremely superfluous, and methanol filled in recent years
Only four one-tenth of the equal utilization of capacity of horizontalization, methanol industry suffers great loss.But since methanol is important industrial chemicals, it can partially replace stone
Oil, with the rise of New Coal Chemical technology in recent years, methanol-to-olefins (ethylene, propylene), methanol aromatic hydrocarbons is by Xinjiang, interior
The favor of the coals main producing regions such as illiteracy, due to having coal price advantage, the large-scale first of tens sets of annual outputs, 500,000 tons of above scales of methanol
Alcohol device has built up or has stepped up to build, and wherein maximum-norm is the middle day conjunction wound year for being located at Ordos, inner Mongolia
Produce 3,600,000 tons of methanol projects.
Deified million tons of DCL/Direct coal liquefaction liquefaction projects of group have been included in the long-term operation stage at present, Lu An group and she
Two sets of annual outputs, 160,000 tons of ICL for Indirect Coal Liquefaction liquefaction projects of safe group have been gone into operation operation, " deify Ning Mei group coal in June, 2011
The report of charcoal indirect liquefaction project application " it is assessed by expert, 4,000,000 tons/year of oil products of Project design production capacity, in March, 2011, by Shan
The northern Shensi chemical industry Energy Base elm of western future source of energy Chemical Co., Ltd. investment horizontal coal cleaning comprehensive utilization one phase of demonstrative project builds
If 1,000,000 tons/year of ICL for Indirect Coal Liquefaction liquefaction demonstration plants.It is expected that the coming years will form ten-million-ton scale coal oil scale.
It is both needed in the devices such as coal oil, natural gas from coal (SNG), large-scale ammonia from coal, coal-ethylene glycol in low-temp methanol
Process outlet setting guard bed is washed, the COS and H of low-temp methanol washing process outlet are further removed2S, partial devices are direct at present
Using common zinc oxide desulfurizing agent, it is only capable of partial removal H2S, cannot remove the COS in gas source, and some devices use depth hydrolysis
Catalyst string depth desulfurizing agent, is first hydrolyzed to H for COS2S, then with depth desulfurizing agent by H2S removing, the depth of synthesis gas are net
What is used in change process patent CN200810046867.5 is exactly this technique, and this technique need to load two kinds of catalyst, a kind of
It hydrolyzing, a kind of desulfurization, equipment need to consider the ratio of height to diameter of every kind of catalyst when designing, cause catalyst entirety ratio of height to diameter excessively high, if
Standby volume is excessive, and excessive so as to cause resistance, the high-tension apparatus cost that admission space increase will lead to 6.0~9.0MPa is excessively high,
If using a kind of inversion absorption type deep purifying desulfurizing agent, while hydrolyzing removing COS and H2S can be reduced equipment volume
One third, to reduce device fabrication expense.
The present invention is directed to low in the devices such as coal oil, natural gas from coal (SNG), large-scale ammonia from coal, coal-ethylene glycol
COS and H in warm methanol cleaning process exiting syngas2S is proposed a kind of while being removed COS and H2The deep purifying fine de-sulfur of S
Agent and preparation method thereof.
Summary of the invention:
The technical problem to be solved by the present invention is to backgrounds in view of the above technology, provide a kind of while removing COS and H2S
Deep purifying desulfurizing agent and preparation method thereof.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of deep purifying desulfurizing agent, the deep purifying desulfurizing agent is by ZnAl2O4, metal oxide and alkali metal
Hydroxide or carbonate form, ZnAl by weight percentage in deep purifying desulfurizing agent finished product2O4Account for 60~90%, gold
Category oxide accounts for 8~30%, alkali metal hydroxide or carbonate accounts for 2~15%.
According to the above scheme, the metal oxide is one of manganese dioxide, lead oxide, molybdenum sesquioxide or more
Combination.
A kind of preparation method of above-mentioned deep purifying desulfurizing agent, preparation step are as follows:
(1) ZnAl is prepared2O4: zinc nitrate and alumina powder are made into aqueous solution respectively, heat in cocurrent addition stirred tank dense
Contracting obtains slurry, and filter cake is dried through overfire air after pressure filtration washing, spare using crushing after 400~450 DEG C of roastings；
(2)ZnAl2O4With metal oxide is dry-mixed stirs evenly, addition is configured to by alkali metal hydroxide or carbonate
Solution, stir evenly, mediate extruded moulding；
(3) it dries in the shade, then through the dry obtained deep purifying desulfurizing agent of hot-air.
Deep purifying desulfurizing agent is obtained by above 3 step.
According to the above scheme, hot-air drying temperature is 110-130 DEG C in the step 1).
According to the above scheme, the time of drying in the shade in the step 3) is 2-12h.
According to the above scheme, 110-130 DEG C of hot-air drying temperature in the step 3), 4-8 hours of drying time
According to the above scheme, the deep purifying desulfurizing agent can export low-temp methanol washing process in room temperature~250 DEG C
COS and H in synthesis gas2S is further removed to equal < 5ppb, protection downstream methanol synthesis, methanation, F- T synthesis, DMO synthesis
Equal catalyst.
The technique that above-mentioned low-temp methanol washing process exiting syngas is handled using above-mentioned deep purifying desulfurizing agent, by coal system
Low-temp methanol washing process exiting syngas is logical in the devices such as oil, natural gas from coal (SNG), large-scale ammonia from coal, coal-ethylene glycol
Enter above-mentioned deep purifying desulfurizing agent bed, carries out COS and H in low-temp methanol washing process exiting syngas2The deep purifying of S is de-
It removes.
According to the above scheme, the removal temperature is 80-200 DEG C, and air speed control is 4000-20000h-1。
This patent the utility model has the advantages that
This patent uses the ZnAl with spinel structure2O4Carrying alkali metal hydroxide or the oxidation of carbonate and metal
Object component will be completed in following two reaction bonded to one interface of spinel structure.
COS+H2O=H2S+CO2
H2S+ZnO=ZnS+H2O
The H that COS hydrolysis generates2S is removed rapidly under the action of catalyst, the product H thus hydrolyzed2S reduction can lead to
COS hydrolysis carries out to the right, and COS hydrolysis efficiency greatly improves；
H2S+ZnO=ZnS+H2O reaction is restricted by balance, reactant H2The equilibrium concentration of S can not be lower than 5ppb, the present invention
It can make unreacted micro H by the preferred addition of metal oxide2The metals such as S and manganese dioxide, lead oxide, molybdenum sesquioxide
Oxide depth is reacted and is removed；
Thus it is successfully realized a kind of product while removing COS and H2S's is difunctional, and has reached COS and H2The depth of S
Purification, it is ensured that remaining COS content < 5ppb；Remaining H2S content < 5ppb.
Specific embodiment
Further summary of the invention of the invention is illustrated with example below:
Embodiment 1:
(1) ZnAl is prepared2O4: 300 grams of zinc nitrates and 102 grams of alumina powders are made into aqueous solution respectively, and cocurrent, which is added, to be used
It is concentrated to get slurry in the stirred tank of jacket steam heating, filter cake is dried by 120 DEG C of hot-airs after pressure filtration washing, using
It is crushed after 450 DEG C of roastings and obtains~180 grams of ZnAl2O4It is spare；
(2) 100 grams of ZnAl are taken2O4With 12 grams of manganese dioxide are dry-mixed stirs evenly, be added and to be configured to by 5 grams of sodium hydroxides
Solution stirs evenly, and mediates extruded moulding；
(3) it dries in the shade 8 hours, it is 6 hours dry in 120 DEG C of hot-airs.
Deep purifying desulfurizing agent 1 is obtained by above 3 step.
Embodiment 2:
(1) ZnAl is prepared2O4: 300 grams of zinc nitrates and 102 grams of alumina powders are made into aqueous solution respectively, and cocurrent, which is added, to be used
It is concentrated to get slurry in the stirred tank of jacket steam heating, filter cake is dried by 120 DEG C of hot-airs after pressure filtration washing, using
It is crushed after 450 DEG C of roastings and obtains~180 grams of ZnAl2O4It is spare；
(2) 100 grams of ZnAl are taken2O4With 30 grams of lead oxide are dry-mixed stirs evenly, addition is configured to molten by 6 grams of potassium hydroxide
Liquid stirs evenly, and mediates extruded moulding；
(3) it dries in the shade 8 hours, it is 6 hours dry in 120 DEG C of hot-airs.
Deep purifying desulfurizing agent 2 are obtained by above 3 step.
Embodiment 3:
(1) ZnAl is prepared2O4: 300 grams of zinc nitrates and 102 grams of alumina powders are made into aqueous solution respectively, and cocurrent, which is added, to be used
It is concentrated to get slurry in the stirred tank of jacket steam heating, filter cake is dried by 110 DEG C of hot-airs after pressure filtration washing, using
It is crushed after 420 DEG C of roastings and obtains~180 grams of ZnAl2O4It is spare；
(2) 100 grams of ZnAl are taken2O4With 18 grams of molybdenum sesquioxides are dry-mixed stirs evenly, be added and to be configured to by 12 grams of sodium carbonate
Solution stirs evenly, and mediates extruded moulding；
(3) it dries in the shade 10 hours, it is 5 hours dry in 130 DEG C of hot-airs.
Deep purifying desulfurizing agent 3 are obtained by above 3 step.
3 samples of above-mentioned preparation are in CO 29%, H267%, CO22%, N21.9%, H2O 0.1%, COS
0.05ppm、H2S 0.05ppm representative cryogenic methanol washes evaluation result such as table 1 in exiting syngas:
Table 1
The T504 room temperature COS hydrolysis that presently commercially available mature fine de-sulfur product has Huashuo Science Co., Ltd to produce is urged
Agent and EZ-2 zinc oxide fine desulfurizer, wherein T504 is mainly organized as alkali metal and activated alumina, and function is COS hydrolysis,
There is no H2S remove；EZ-2 is mainly organized as activated zinc oxide and binder, and function is H2S removing, and remove precision and be
0.1ppm does not have COS hydrolysis function.Both products are in CO 29%, H267%, CO22%, N21.9%, H2O 0.1%,
COS 0.05ppm、H2S 0.05ppm representative cryogenic methanol washes evaluation result such as table 2 in exiting syngas:
Table 2
As can be seen from Table 2, the function of T504 COS Hydrolysis Catalyst at Normal Atmospheric Temperature is COS hydrolysis, but hydrolysis efficiency is not
Height, as air speed improves, hydrolysis efficiency can be deteriorated, without H2S remove；The function of EZ-2 zinc oxide fine desulfurizer is H2S is de-
It removes, but removing precision is not high, as air speed improves, H2S removing precision can be deteriorated difference, not have COS hydrolysis function.
By presently commercially available mature fine de-sulfur product T504 COS Hydrolysis Catalyst at Normal Atmospheric Temperature and EZ-2 zinc oxide fine desulfurizer group
It closes and uses, make CO 29%, H267%, CO22%, N21.9%, H2O 0.1%, COS 0.05ppm, H2S 0.05ppm is typical
Low-temp methanol, which washes exiting syngas and first passes through T504 COS Hydrolysis Catalyst at Normal Atmospheric Temperature, hydrolyzes COS, then de- by EZ-2 zinc oxide essence
Sulphur agent is by H2S removing, evaluation result such as table 3:
Table 3
As seen from Table 3, T504 COS Hydrolysis Catalyst at Normal Atmospheric Temperature and EZ-2 zinc oxide fine desulfurizer are applied in combination, in not equality of temperature
It spends and using outlet COS and H under space velocities2S is unable to reach the effect of deep purifying.
Claims (8)
1. a kind of deep purifying desulfurizing agent, it is characterised in that: the deep purifying desulfurizing agent is by ZnAl2O4, metal oxide,
And alkali metal hydroxide or carbonate form, ZnAl by weight percentage in deep purifying desulfurizing agent finished product2O4Account for 60
~ 90%, metal oxide accounts for 8 ~ 30%, alkali metal hydroxide or carbonate accounts for 2 ~ 15%；The metal oxide is titanium dioxide
One of manganese, lead oxide, molybdenum sesquioxide or above combination.
2. the preparation method of deep purifying desulfurizing agent described in claim 1, it is characterised in that: preparation step is as follows:
(1) ZnAl is prepared2O4: zinc nitrate and alumina powder are made into aqueous solution respectively, and cocurrent is added in stirred tank to heat and be concentrated to give
To slurry, filter cake is dried through overfire air after pressure filtration washing, spare using crushing after 400 ~ 450 DEG C of roastings；
(2) ZnAl2O4With metal oxide is dry-mixed stirs evenly, addition is configured to molten by alkali metal hydroxide or carbonate
Liquid stirs evenly, and mediates extruded moulding；
(3) it dries in the shade, then through the dry obtained deep purifying desulfurizing agent of hot-air.
3. the preparation method of deep purifying desulfurizing agent according to claim 2, it is characterised in that: in the step (1)
Hot-air drying temperature is 110-130 DEG C.
4. the preparation method of deep purifying desulfurizing agent according to claim 2, it is characterised in that: in the step (3)
Dry in the shade the time be 2-12h.
5. the preparation method of deep purifying desulfurizing agent according to claim 2, it is characterised in that: in the step (3)
110-130 DEG C of air drying temp, drying time 4-8 hours.
6. the preparation method of deep purifying desulfurizing agent according to claim 2, it is characterised in that: the deep purifying
Desulfurizing agent can be in room temperature ~ 250 DEG C, by COS and H in low-temp methanol washing process exiting syngas2S is further removed to equal <
5ppb protects downstream methanol synthesis, methanation, F- T synthesis, DMO synthetic catalyst.
7. using the technique of deep purifying desulfurizing agent processing low-temp methanol washing process exiting syngas described in claim 1,
It is characterized by: low-temp methanol washing process in coal oil, natural gas from coal, large-scale ammonia from coal, coal-ethylene glycol device is gone out
Mouth synthesis gas is passed through above-mentioned deep purifying desulfurizing agent bed, carries out COS and H in low-temp methanol washing process exiting syngas2S's
Deep purifying removing.
8. technique according to claim 7, it is characterised in that: the removal temperature is 80-200 DEG C, and air speed control is
4000-20000h-1。
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| CN201610536607.0A CN106179328B (en) | 2016-07-08 | 2016-07-08 | A kind of deep purifying desulfurizing agent and preparation method thereof |
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| CN118320811B (en) * | 2024-06-14 | 2024-10-18 | 北京化工大学 | Hydrotalcite-based carbonyl sulfide hydrolysis catalyst, preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0747120A2 (en) * | 1995-06-07 | 1996-12-11 | Phillips Petroleum Company | Particulate compositions |
| WO2002022763A1 (en) * | 2000-09-11 | 2002-03-21 | Research Triangle Institute | Process for desulfurizing hydrocarbon fuels and fuel components |
| CN101119796A (en) * | 2005-01-06 | 2008-02-06 | 研究三角协会 | Zinc oxide based adsorption agent and method of making and using same |
| CN101287546A (en) * | 2005-09-27 | 2008-10-15 | 研究三角协会 | Regenerable sorbents for removal of sulfur from hydrocarbons and processes for their preparation and use |
| CN101747931A (en) * | 2010-01-12 | 2010-06-23 | 华烁科技股份有限公司 | Fine desulfurizing agent for transforming thioalcohol in liquid hydrocarbons at normal temperature and preparation and application methods thereof |
| CN101885981A (en) * | 2010-07-13 | 2010-11-17 | 华烁科技股份有限公司 | Fine desulfurizer used for removing thiol from liquid hydrocarbon at normal temperature, preparation method thereof and application method thereof |
| CN104475112A (en) * | 2014-12-15 | 2015-04-01 | 华烁科技股份有限公司 | Catalyst capable of catalyzing and decomposing N2O under high-temperature water-oxygen supplying condition and preparation method of catalyst |
-
2016
- 2016-07-08 CN CN201610536607.0A patent/CN106179328B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0747120A2 (en) * | 1995-06-07 | 1996-12-11 | Phillips Petroleum Company | Particulate compositions |
| WO2002022763A1 (en) * | 2000-09-11 | 2002-03-21 | Research Triangle Institute | Process for desulfurizing hydrocarbon fuels and fuel components |
| CN101119796A (en) * | 2005-01-06 | 2008-02-06 | 研究三角协会 | Zinc oxide based adsorption agent and method of making and using same |
| CN101287546A (en) * | 2005-09-27 | 2008-10-15 | 研究三角协会 | Regenerable sorbents for removal of sulfur from hydrocarbons and processes for their preparation and use |
| CN101747931A (en) * | 2010-01-12 | 2010-06-23 | 华烁科技股份有限公司 | Fine desulfurizing agent for transforming thioalcohol in liquid hydrocarbons at normal temperature and preparation and application methods thereof |
| CN101885981A (en) * | 2010-07-13 | 2010-11-17 | 华烁科技股份有限公司 | Fine desulfurizer used for removing thiol from liquid hydrocarbon at normal temperature, preparation method thereof and application method thereof |
| CN104475112A (en) * | 2014-12-15 | 2015-04-01 | 华烁科技股份有限公司 | Catalyst capable of catalyzing and decomposing N2O under high-temperature water-oxygen supplying condition and preparation method of catalyst |
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