CN106179328A - 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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- CN106179328A CN106179328A CN201610536607.0A CN201610536607A CN106179328A CN 106179328 A CN106179328 A CN 106179328A CN 201610536607 A CN201610536607 A CN 201610536607A CN 106179328 A CN106179328 A CN 106179328A
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- desulfurizing agent
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 37
- 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 39
- 238000005406 washing Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001676 gahnite Inorganic materials 0.000 claims abstract description 8
- 239000003245 coal Substances 0.000 claims description 24
- 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
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 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
- 239000000843 powder Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 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
- 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
- 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
- 125000005587 carbonate group Chemical group 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
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 description 17
- 238000006460 hydrolysis reaction Methods 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 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
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000000376 reactant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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 agent and preparation method thereof.This 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 60～90%, metal-oxide account for 8～30%, alkali metal hydroxide or carbonate account for 2～15%.The deep purifying desulfurizing agent that the present invention provides can be by COS and H in low-temp methanol washing process exiting syngas2S is removed to the catalyst such as equal ＜ 5ppb, protection downstream methanol synthesis, methanation, F-T synthesis, DMO synthesis further.
Description
Technical field:
The present invention relates to remove COS and H2The technical field of S, particularly relates at coal liquifaction, natural gas from coal (SNG), big
In the devices such as type ammonia from coal, coal-ethylene glycol, removing low-temp methanol washing process exports COS and H further2The deep purifying essence of S
Desulfurizing agent.
Background technology:
At present, family more than 270 of methanol enterprise of China, production capacity, more than 50,000,000 tons, accounts for the 46.8% of world's production capacity.Thus may be used
Seeing, average Mei Jia enterprise methanol production capacity is less than 200,000 tons.2006-2008 methanol prices sharp rises and causes a large amount of methanol project
Starting, from 2009, due to the impact of world financial crisis, methanol prices is low, and production capacity is superfluous, in recent years methanol dress
The equal utilization of capacity of horizontalization only four one-tenth, methanol industry suffers great loss.But owing to methanol is important industrial chemicals, can partly replace stone
Oil, along 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 coal main producing regions such as illiteracy, owing to there being coal price advantage, the large-scale first of 500,000 tons of above scales of methanol produced per year by tens sets
Alcohol device has built up or has stepped up to build, and wherein maximum-norm is that the middle sky being seated in Ordos, inner Mongolia closes wound year
Produce 3,600,000 tons of methanol projects.
Deify at present million tons of DCL/Direct coal liquefaction liquefaction projects of group and counted the long-term operation stage, Lu An group and she
Two sets of safe group are produced 160000 tons of ICL for Indirect Coal Liquefaction liquefaction projects per year and have been gone into operation operations, in June, 2011, " deified Ning Mei group coal
Charcoal indirect liquefaction project application is reported " to be assessed by expert, 4,000,000 tons/year of oil products of Project design production capacity, in March, 2011, by Shan
Northern Shensi chemical industry Energy Base elm horizontal coal cleaning comprehensive utilization demonstrative project one phase of western future source of energy Chemical Co., Ltd. investment builds
If 1,000,000 tons/year of ICL for Indirect Coal Liquefaction liquefaction demonstration plants.The anticipated coming years will form ten-million-ton scale coal liquifaction scale.
The devices such as coal liquifaction, natural gas from coal (SNG), large-scale ammonia from coal, coal-ethylene glycol are both needed at low-temp methanol
Wash process outlet and guard bed is set, further COS and H of removing low-temp methanol washing process outlet2S, current partial devices is direct
Use common zinc oxide desulfurizing agent, be only capable of partial removal H2S, it is impossible to the COS in removing source of the gas, some devices use depth hydrolysis
Catalyst string degree of depth desulfurizing agent, is first hydrolyzed to H by COS2S, then with degree of depth desulfurizing agent by H2S removes, and the degree of depth of synthesis gas is clean
Use in change process patent CN200810046867.5 is exactly this technique, and this technique need to load two kinds of catalyst, a kind of
Hydrolysis, a kind of desulfurization, the ratio of height to diameter of every kind of catalyst need to be considered during equipment design, cause catalyst entirety ratio of height to diameter too high, if
Standby volume is excessive, thus causes resistance excessive, admission space increase can cause 6.0～9.0MPa high pressure equipment cost too high,
If using a kind of inversion absorption type deep purifying desulfurizing agent, COS and H of hydrolysis removing simultaneously2S, can reduce equipment volume
1/3rd, thus reduce device fabrication expense.
The present invention is directed in the devices such as coal liquifaction, natural gas from coal (SNG), large-scale ammonia from coal, coal-ethylene glycol low
COS and H in temperature methanol cleaning process exiting syngas2S, it is proposed that one removes COS and H simultaneously2The deep purifying fine de-sulfur of S
Agent and preparation method thereof.
Summary of the invention:
The technical problem to be solved is for above-mentioned technical background, it is provided that one removes COS and H simultaneously2S
Deep purifying desulfurizing agent and preparation method thereof.
For solving above-mentioned technical problem, the present invention adopts the following technical scheme that
A kind of deep purifying desulfurizing agent, this 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 60～90%, gold
Belong to oxide account for 8～30%, alkali metal hydroxide or carbonate account for 2～15%.
By such scheme, described metal-oxide is one or more in manganese dioxide, lead oxide, molybdenum sesquioxide
Combination.
A kind of preparation method of above-mentioned deep purifying desulfurizing agent, preparation process is as follows:
(1) ZnAl is prepared2O4: zinc nitrate and alumina powder are made into aqueous solution respectively, and flow addition stirred tank heats dense
Contracting obtains slurry, and after filter pressing washing, filter cake is through hot air dries, then pulverizes standby after 400～450 DEG C of roastings；
(2)ZnAl2O4It is dry mixed with metal-oxide and stirs, add and be configured to by alkali metal hydroxide or carbonate
Solution, stir, mediate extruded moulding；
(3) dry in the shade, then prepare deep purifying desulfurizing agent through hot-air dry.
Deep purifying desulfurizing agent is i.e. prepared through above 3 steps.
By such scheme, described step 1) in hot air dries temperature be 110-130 DEG C.
By such scheme, described step 3) in the time of drying in the shade be 2-12h.
By such scheme, described step 3) in hot air dries temperature 110-130 DEG C, drying time 4-8 hour.
By such scheme, low-temp methanol washing process can be exported by described deep purifying desulfurizing agent room temperature～250 DEG C
COS and H in synthesis gas2S is removed to equal ＜ 5ppb, protection downstream methanol synthesis, methanation, F-T synthesis, DMO synthesis further
Deng catalyst.
Above-mentioned deep purifying desulfurizing agent is utilized to process the technique of above-mentioned low-temp methanol washing process exiting syngas, by coal system
In the device such as oil, natural gas from coal (SNG), large-scale ammonia from coal, coal-ethylene glycol, low-temp methanol washing process exiting syngas leads to
Enter above-mentioned deep purifying desulfurizing agent bed, carry out COS and H in low-temp methanol washing process exiting syngas2The deep purifying of S takes off
Remove.
By such scheme, described removal temperature is 80-200 DEG C, and air speed controls as 4000-20000h-1。
The beneficial effect of this patent:
This patent uses the ZnAl with spinel structure2O4Carrying alkali metal hydroxide or carbonate and burning
Thing component, completes following two reaction bonded on one interface of spinel structure.
COS+H2O=H2S+CO2
H2S+ZnO=ZnS+H2O
The H that COS hydrolysis produces2S removes rapidly under catalyst action, the product H thus hydrolyzed2S minimizing may result in
COS hydrolysis is carried out to the right, and COS hydrolysis efficiency is greatly improved；
H2S+ZnO=ZnS+H2O reaction is restricted by balance, reactant H2The equilibrium concentration of S cannot be less than 5ppb, the present invention
Unreacted trace H can be made by the preferably interpolation 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 and removes COS and H simultaneously2S's is difunctional, and has reached COS and H2The degree of depth of S
Purify, it is ensured that residue COS content ＜ 5ppb；Residue H2S content ＜ 5ppb.
Detailed description of the invention
Further the summary of the invention of the present 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 flow addition employing
Being concentrated to give slurry in the stirred tank of jacket steam heating, after filter pressing washing, filter cake is through 120 DEG C of hot air dries, then passes through
Pulverize after 450 DEG C of roastings and obtain～180 grams of ZnAl2O4Standby；
(2) 100 grams of ZnAl are taken2O4Being dry mixed with 12 grams of manganese dioxide and stir, addition is configured to by 5 grams of sodium hydroxide
Solution, stirs, and mediates extruded moulding；
(3) dry in the shade 8 hours, 120 DEG C of hot-air dries 6 hours.
Deep purifying desulfurizing agent 1 is i.e. prepared through above 3 steps.
Embodiment 2:
(1) ZnAl is prepared2O4: 300 grams of zinc nitrates and 102 grams of alumina powders are made into aqueous solution respectively, and flow addition employing
Being concentrated to give slurry in the stirred tank of jacket steam heating, after filter pressing washing, filter cake is through 120 DEG C of hot air dries, then passes through
Pulverize after 450 DEG C of roastings and obtain～180 grams of ZnAl2O4Standby；
(2) 100 grams of ZnAl are taken2O4Be dry mixed with 30 grams of lead oxide and stir, add by 6 grams of potassium hydroxide be configured to molten
Liquid, stirs, and mediates extruded moulding；
(3) dry in the shade 8 hours, 120 DEG C of hot-air dries 6 hours.
Deep purifying desulfurizing agent 2 is i.e. prepared through above 3 steps.
Embodiment 3:
(1) ZnAl is prepared2O4: 300 grams of zinc nitrates and 102 grams of alumina powders are made into aqueous solution respectively, and flow addition employing
Being concentrated to give slurry in the stirred tank of jacket steam heating, after filter pressing washing, filter cake is through 110 DEG C of hot air dries, then passes through
Pulverize after 420 DEG C of roastings and obtain～180 grams of ZnAl2O4Standby；
(2) 100 grams of ZnAl are taken2O4Being dry mixed with 18 grams of molybdenum sesquioxides and stir, addition is configured to by 12 grams of sodium carbonate
Solution, stirs, and mediates extruded moulding；
(3) dry in the shade 10 hours, 130 DEG C of hot-air dries 5 hours.
Deep purifying desulfurizing agent 3 is i.e. prepared through above 3 steps.
3 samples of above-mentioned preparation are at 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 ripe fine de-sulfur product has Huashuo Science Co., Ltd to produce is urged
Agent and EZ-2 zinc oxide fine desulfurizer, wherein T504 mainly comprises as alkali metal and activated alumina, and function is COS hydrolysis,
There is no H2S remove；EZ-2 mainly comprises as activated zinc oxide and binding agent, and function is H2S removes, and removing precision is
0.1ppm, does not has COS hydrolysis function.Both products are at 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, along with air speed improves, hydrolysis efficiency can be deteriorated, not have H2S remove；The function of EZ-2 zinc oxide fine desulfurizer is H2S takes off
Remove, but removing precision is the highest, along with air speed improves, H2S removing precision can be deteriorated difference, does not has COS hydrolysis function.
By presently commercially available ripe fine de-sulfur product T504 COS Hydrolysis Catalyst at Normal Atmospheric Temperature and EZ-2 zinc oxide fine desulfurizer group
Close and use, make CO 29%, H267%, CO22%, N21.9%, H2O 0.1%, COS 0.05ppm, H2S 0.05ppm typical case
Low-temp methanol is washed exiting syngas and is first passed through T504 COS Hydrolysis Catalyst at Normal Atmospheric Temperature and hydrolyzed by COS, then by EZ-2 zinc oxide loss of essence
Sulfur agent is by H2S removes, 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
COS and H is exported under degree and use space velocities2S is all unable to reach the effect of deep purifying.
Claims (9)
1. a deep purifying desulfurizing agent, it is characterised in that: this 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 account for 8～30%, alkali metal hydroxide or carbonate account for 2～15%.
Deep purifying desulfurizing agent the most according to claim 1, it is characterised in that: described metal-oxide is titanium dioxide
One or more combination in manganese, lead oxide, molybdenum sesquioxide.
3. the preparation method of the deep purifying desulfurizing agent described in claim 1, it is characterised in that: preparation process is as follows:
(1) ZnAl is prepared2O4: zinc nitrate and alumina powder are made into aqueous solution respectively, and flow to heat in addition stirred tank and be concentrated to give
To slurry, after filter pressing washing, filter cake is through hot air dries, then pulverizes standby after 400～450 DEG C of roastings；
(2)ZnAl2O4Be dry mixed with metal-oxide and stir, add by alkali metal hydroxide or carbonate be configured to molten
Liquid, stirs, and mediates extruded moulding；
(3) dry in the shade, then prepare deep purifying desulfurizing agent through hot-air dry.
The preparation method of deep purifying desulfurizing agent the most according to claim 3, it is characterised in that: described step 1) in heat
Air is dried temperature and is 110-130 DEG C.
The preparation method of deep purifying desulfurizing agent the most according to claim 3, it is characterised in that: described step 3) in
The time of drying in the shade is 2-12h.
The preparation method of deep purifying desulfurizing agent the most according to claim 3, it is characterised in that: described step 3) in
Hot air dries temperature 110-130 DEG C, drying time 4-8 hour.
The preparation method of deep purifying desulfurizing agent the most according to claim 3, it is characterised in that: described deep purifying
Desulfurizing agent can be room temperature～250 DEG C, by COS and H in low-temp methanol washing process exiting syngas2S is removed to equal ＜ further
5ppb, protects the catalyst such as downstream methanol synthesis, methanation, F-T synthesis, DMO synthesis.
8. utilize the deep purifying desulfurizing agent described in claim 1 to process the technique of low-temp methanol washing process exiting syngas,
It is characterized in that: low-temp methanol washing process in coal liquifaction, 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 removes.
Technique the most according to claim 8, it is characterised in that: described removal temperature is 80-200 DEG C, and air speed control is
4000-20000h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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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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| 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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| CN106179328A true CN106179328A (en) | 2016-12-07 |
| CN106179328B CN106179328B (en) | 2019-01-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110564457A (en) * | 2019-07-26 | 2019-12-13 | 沈阳三聚凯特催化剂有限公司 | Deep purification fine desulfurizer and preparation method thereof |
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