CN110144250A - The preparation method of organic sulfur compound scavenger in a kind of fuel - Google Patents
The preparation method of organic sulfur compound scavenger in a kind of fuel Download PDFInfo
- Publication number
- CN110144250A CN110144250A CN201910292039.8A CN201910292039A CN110144250A CN 110144250 A CN110144250 A CN 110144250A CN 201910292039 A CN201910292039 A CN 201910292039A CN 110144250 A CN110144250 A CN 110144250A
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- China
- Prior art keywords
- preparation
- organic sulfur
- desulfurizing agent
- ion
- dipping
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The purpose of the present invention is improving the adsorption capacity and selectivity of organic sulfur compound in natural gas, a kind of preparation method of desulfurizing agent for natural gas fine de-sulfur is provided.The method that the present invention uses is: coaly activated carbon uses for principle with the compound pretreatment of Acid-Base-surfactant, then prepares new composite adsorbent, the organic sulfur in adsorbing and removing gas using complexing agent complexing impregnating metal ion.The compound adsorbent of this method preparation has excellent absorption property to the organic sulfur in gas, and organic sulfur compound content is 10mg/m after absorption3Below.Desulfurizing agent of the invention is selectively strong to sulfide, and equipment is simple, and investment is low, has applications well prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of organic sulfur compound scavenger for gas fuel field of refinement.
Background technique
Due to its low in cost, high-efficiency environment friendly, green many advantages, such as cleaning, has become natural gas in fossil energy
One of the main energy sources of human society application at present.Natural gas is mainly made of hydrocarbon-alkane, also containing a small amount of miscellaneous
Matter such as H2S, CO2 and small part organic sulfur.Wherein, organic sulfur includes carbon disulfide (CS2), mercaptan (RSH), carbonyl sulfur
(COS), thioether (RSR) and disulfide (RSSR) etc..It, can be to the pipe in storage and transportation process when containing sulfide in natural gas
It causes to corrode in road.The gases such as SO2 can be generated after sulfur-containing gas burning and cause acid rain, and environmental pollution is serious.By a series of
Physics, chemical means carry out desulfurization process to natural gas, have not only met the requirement of Green Chemistry, but also have to the protection of ecological environment
Significance.Solvent method has desulfuration efficiency height, the big advantage of capacity, but has equipment investment big simultaneously, and use cost is high
The shortcomings that.Adsorbent method has preparation simple, and the advantages such as equipment investment is small, and operating cost is low are the development of natural gas fine de-sulfur
Direction.But the generally existing adsorption capacity of adsorption desulfurizing agent is small at present, regenerates difficult problem, limits the application of absorption method.Cause
To natural gas fine purification, the industrial circles such as gas sweetening are of great significance the adsorbent of this exploitation high-adsorption-capacity.
Summary of the invention
The purpose of the present invention is improving the adsorption capacity and selectivity of organic sulfur compound in natural gas, provide a kind of for day
The preparation method of the desulfurizing agent of right gas fine de-sulfur.To achieve the goals above, the method that the present invention uses is: coaly activated carbon for
Principle is used with the compound pretreatment of Acid-Base-surfactant, is then prepared using complexing agent complexing impregnating metal ion novel
Compound adsorbent, the organic sulfur in adsorbing and removing gas.
Technical solution of the present invention are as follows:
Raw material active carbon is activated into 4h in 80 DEG C of vacuum oven first, with sodium hydrate aqueous solution alkali process 1-5
Hour, then in mixture of hydrochloric acid and nitric acid (hydrochloric acid: the volume ratio of nitric acid is 5:1~1:5) at 1-10 hours progress acid of processing
Reason.Above-mentioned pretreated material is utilized into complexing ligand such as ammonium hydroxide, citrate, pyrophosphate, sulphur using impregnating by pressure
One of thiosulfate, sulphite or a variety of assisting ions dipping, the ion of dipping include iron, cobalt, nickel, copper, zinc, silver,
One of tin is a variety of, and 80-140 DEG C of dipping temperature, dip time is 2-48 hours.Material after dipping is done by washing
Organic sulfur absorbent is prepared in dry, roasting.
For removing the laboratory evaluation of the composite desulfurizing agent desulfurization performance of organic sulfur in natural gas: according to above scheme system
Standby desulfurizing agent is to containing 200mg/m3A desulfurization is fixed in the natural gas of organic sulfur compound, in filling 0.5g absorption
Agent, organic sulfur compound content is 10mg/m after absorption3Below.After adsorption saturation, using being exported after being reused 4 times after hot recycling
Organic sulfur compound content is in 10mg/m3 or less.Regeneration effect is good, and adsorbent may be reused.
The present invention is compared with the prior art, and is modified to existing common organic sulfur absorbent and compound take off is prepared
Then sulphur agent increases the dipping effect of ion using complexing agent auxiliary complexing using the compound pretreatment of Acid-Base, can make from
Son is deep into inside duct, adsorption activity position ratio is improved, so to organic sulfur compound according to highly selective and high sulfur capacity.Second phase is originally
All there is unoccupied orbital in the ion that invention uses, have adsorption capacity to sulfide.And active carbon is at low cost, with material all
It is conventional material, so that adsorbent cost is low, organic sulfur industrial application.Therefore desulfurizing agent of the invention is to sulfide selectivity
By force, capacity is big, and equipment is simple, and investment is low, has applications well prospect.
Specific embodiment
The following describes the present invention in detail with reference to examples:
Embodiment one:
Raw material active carbon is activated into 4h in 80 DEG C of vacuum oven, it is small with 2% sodium hydrate aqueous solution alkali process 3
When, acid processing in 3 hours is then carried out in mixture of hydrochloric acid and nitric acid (hydrochloric acid: the volume ratio of nitric acid is 1:1).It will be above-mentioned pre-
Treated material is that complexing ligand assisting ion impregnates using citrate using impregnating by pressure, the ion of dipping be nickel and
Copper, the dosage of ion are 1% of quality of activated carbon after pretreatment, and the mass ratio of the material of complexing agent and ion is 2:1.Dipping temperature
120 DEG C, dip time is 12 hours.Material after dipping, by washing, organic sulfur absorbent is prepared in dry, roasting.
The desulfurization performance laboratory evaluation of the organic sulfur composite desulfurizing agent prepared according to the method described above is as follows: according to top
A desulfurization, filling 0.5g absorption is fixed to the natural gas containing 200mg/m3 organic sulfur compound in the desulfurizing agent of case preparation
Agent, measuring outlet organic sulfur compound content is 10mg/m3Below.
Embodiment two:
Raw material active carbon is activated into 4h in 80 DEG C of vacuum oven, it is small with 5% sodium hydrate aqueous solution alkali process 3
When, acid processing in 4 hours is then carried out in mixture of hydrochloric acid and nitric acid (hydrochloric acid: the volume ratio of nitric acid is 2:1).It will be above-mentioned pre-
Treated material is that complexing ligand assisting ion impregnates using ammonium hydroxide using impregnating by pressure, and the ion of dipping is nickel and copper,
The dosage of ion is 0.5% of quality of activated carbon after pretreatment, and the mass ratio of the material of complexing agent and ion is 1:1.Dipping temperature
120 DEG C, dip time is 20 hours.Material after dipping, by washing, organic sulfur absorbent is prepared in dry, roasting.
The desulfurization performance laboratory evaluation of the organic sulfur composite desulfurizing agent prepared according to the method described above is as follows: according to top
A desulfurization, filling 0.5g absorption is fixed to the natural gas containing 200mg/m3 organic sulfur compound in the desulfurizing agent of case preparation
Agent, measuring outlet organic sulfur compound content is 10mg/m3Below.
Embodiment three:
Raw material active carbon is activated into 4h in 80 DEG C of vacuum oven, it is small with 2% sodium hydrate aqueous solution alkali process 1
When, acid processing in 1 hour is then carried out in mixture of hydrochloric acid and nitric acid (hydrochloric acid: the volume ratio of nitric acid is 2:1).It will be above-mentioned pre-
Treated material is that complexing ligand assisting ion impregnates using thiosulfate, the ion of dipping is silver using impregnating by pressure
And copper, the dosage of ion are 1% of quality of activated carbon after pretreatment, the mass ratio of the material of complexing agent and ion is 1:1.Dipping temperature
120 DEG C of degree, dip time are 10 hours.Material after dipping, by washing, organic sulfur absorption is prepared in dry, roasting
Agent.
The desulfurization performance laboratory evaluation of the organic sulfur composite desulfurizing agent prepared according to the method described above is as follows: according to top
A desulfurization, filling 0.5g absorption is fixed to the natural gas containing 200mg/m3 organic sulfur compound in the desulfurizing agent of case preparation
Agent, measuring outlet organic sulfur compound content is 10mg/m3Below.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (7)
1. the preparation method of organic sulfur compound adsorption desulfurizing agent in a kind of natural gas, it is characterized in that:
Raw material active carbon is activated into 4h in 80 DEG C of vacuum oven first, with sodium hydrate aqueous solution alkali process 1-5 hours,
Then acid processing 1-10 hours is handled in mixture of hydrochloric acid and nitric acid, by above-mentioned pretreated material, using impregnating by pressure,
Dipping is completed in active duct using complexing ligand assistant metal ion, dipping temperature is 80-140 DEG C, dip time 2-
48 hours, the material after dipping was dry, roast under controlled atmosphere and organic sulfur is prepared within 2-10 hours inhales by washing
Attached dose, maturing temperature is 100 DEG C -800 DEG C.
2. the preparation method of desulfurizing agent according to claim 1, which is characterized in that hydrogen in sodium hydrate aqueous solution used
The concentration of sodium oxide molybdena is 1%-20%.
3. in the preparation method of desulfurizing agent according to claim 1, which is characterized in that mixture of hydrochloric acid and nitric acid used
Volume ratio for hydrochloric acid and nitric acid is between 5:1 to 1:5.
4. the preparation method of desulfurizing agent according to claim 1, which is characterized in that impregnating by pressure used is in water heating kettle
Middle progress, in temperature-rise period water vapor generate from pressure.
5. the preparation method of desulfurizing agent according to claim 1, which is characterized in that complexing ligand used is ammonium hydroxide, lemon
One of lemon hydrochlorate, pyrophosphate, thiosulfate, sulphite are a variety of.
6. the preparation method of desulfurizing agent according to claim 1, which is characterized in that the ion of dipping used include iron,
One of cobalt, nickel, copper, zinc, silver, tin are a variety of, and the dosage for impregnating ion is the 0.1%- of quality of activated carbon after pretreatment
2%.
7. the preparation method of desulfurizing agent according to claim 1, which is characterized in that complexing agent usage amount according to complexing agent with
The mass ratio of the material of the ratio-dependent of metal ion, complexing agent and ion is 1:2 to 3:1.
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| CN201910292039.8A CN110144250A (en) | 2019-04-12 | 2019-04-12 | The preparation method of organic sulfur compound scavenger in a kind of fuel |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403254A (en) * | 2020-11-20 | 2021-02-26 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
| CN113058550A (en) * | 2021-03-22 | 2021-07-02 | 卡伯恩(苏州)复合材料有限公司 | Carbon aerogel microsphere for adsorbing carbonyl sulfide and mercury and preparation method thereof |
| CN113877529A (en) * | 2021-11-02 | 2022-01-04 | 浙江工业大学 | Preparation method and desulfurization application of cobalt-doped carbon aerogel |
| CN116078347A (en) * | 2022-12-23 | 2023-05-09 | 大连理工大学 | Preparation method of Cu (I)/ZSM-5 desulfurizing agent and application of desulfurizing agent in removal of carbonyl sulfide in gas |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403254A (en) * | 2020-11-20 | 2021-02-26 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
| CN112403254B (en) * | 2020-11-20 | 2022-09-27 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
| CN113058550A (en) * | 2021-03-22 | 2021-07-02 | 卡伯恩(苏州)复合材料有限公司 | Carbon aerogel microsphere for adsorbing carbonyl sulfide and mercury and preparation method thereof |
| CN113058550B (en) * | 2021-03-22 | 2024-10-22 | 卡伯恩(苏州)复合材料有限公司 | Carbon aerogel microsphere for adsorbing carbonyl sulfide and mercury and preparation method thereof |
| CN113877529A (en) * | 2021-11-02 | 2022-01-04 | 浙江工业大学 | Preparation method and desulfurization application of cobalt-doped carbon aerogel |
| CN116078347A (en) * | 2022-12-23 | 2023-05-09 | 大连理工大学 | Preparation method of Cu (I)/ZSM-5 desulfurizing agent and application of desulfurizing agent in removal of carbonyl sulfide in gas |
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Application publication date: 20190820 |