CN115501731B - For removing H from sulfur-containing gases2S absorption liquid, preparation method and application - Google Patents

For removing H from sulfur-containing gases2S absorption liquid, preparation method and application Download PDF

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CN115501731B
CN115501731B CN202110631321.1A CN202110631321A CN115501731B CN 115501731 B CN115501731 B CN 115501731B CN 202110631321 A CN202110631321 A CN 202110631321A CN 115501731 B CN115501731 B CN 115501731B
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absorption liquid
triazine
sulfur
diazabicyclo
gas
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CN115501731A (en
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余勇
陈小花
陈园园
宋丽
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/2041—Diamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20452—Cyclic amines containing a morpholine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053—Other nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention relates to an absorption liquid for removing H 2 S from sulfur-containing gas, a preparation method and application thereof. The absorption liquid comprises the following components in percentage by weight: 10 to 18wt%, preferably 13 to 15wt% triazine; 1 to 5wt%, preferably 2.5 to 4wt%, of a sterically hindered amine; 0.1 to 1wt%, preferably 0.6 to 0.8wt% of an additive; and the balance water. Compared with the traditional desulfurization absorption liquid, the absorption liquid for removing H 2 S has the advantages of high sulfur removal efficiency, large sulfur capacity and small consumption, and simultaneously has the properties of scale inhibition and corrosion inhibition, thereby achieving the purpose of improving economic benefit.

Description

Absorption liquid for removing H 2 S from sulfur-containing gas, preparation method and application
Technical Field
The invention belongs to the field of gas purification, and particularly relates to an absorption liquid for removing H 2 S from sulfur-containing gas, a preparation method and application.
Background
Sulfur-containing natural gas must be stripped of sulfides such as H 2 S to the corresponding specifications (e.g., GB 17820-2018) before it can be piped and used by downstream users. For removing H 2 S in natural gas, a relatively complete process technology has been developed at home and abroad, and a process system taking an alcohol amine absorption method as a main material and a wet oxidation method as an auxiliary material is formed. These process technologies have better technical economics for the desulfurization and purification of natural gas with larger amounts of latent sulfur, but for gas wells or sites with less than 200kg/d, especially 50kg/d, especially low H 2 S gas wells and oilfield associated gas in remote areas, offshore water and gas or with limited space, the alcohol amine absorption process or wet oxidation process is not only technically economically viable but even does not have enough space to build up the plant or provide corresponding utility for the plant operation. Therefore, for the low H 2 S natural gas or oilfield associated gas removal H 2 S conditions, there is a need to develop and use desulfurizing agents and related processes that differ from conventional absorption methods.
Currently, triazine liquid removal agents have been the first technology to remove low concentrations of hydrogen sulfide. The 1,3, 5-tri (2-hydroxyethyl) -hexahydro-s-triazine is widely used, but is easy to produce scaling and corrode pipelines due to the characteristics of high absorption efficiency, small consumption, high speed, small pollution of absorption products and the like when being used for removing hydrogen sulfide.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel absorption liquid for removing H 2 S from sulfur-containing gas (such as low-sulfur natural gas or low-sulfur oilfield associated gas). The absorption liquid has better absorption effect on H 2 S than the traditional absorption liquid, has less consumption, and has the performances of scale inhibition and corrosion inhibition.
To this end, the first aspect of the present invention provides an absorption liquid for removing H 2 S from a sulfur-containing gas, comprising the following components in weight percent:
10 to 18wt% of a triazine;
1 to 5wt%, preferably 2.5 to 4wt%, of a sterically hindered amine;
0.1 to 1wt%, preferably 0.6 to 0.8wt% of an additive; and
The balance of water.
In some embodiments of the present invention, the triazine may be present in the absorption liquid in an amount of 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, etc., in weight percent. In some preferred embodiments of the invention, the triazine content in the absorption liquid is 13 to 15wt%.
In some embodiments of the invention, the triazine is 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
In other embodiments of the invention, the sterically hindered amine comprises at least one of diazabicyclo and morpholine; preferably including diazabicyclo and morpholine.
The inventors of the present application have found through studies that the absorption amount and absorption rate of H 2 S by an absorption liquid can be increased by adding a sterically hindered amine to the absorption liquid. Further, when the hindered amine includes both diazabicyclo and morpholine, the absorption performance of the absorption liquid may be optimized.
In some embodiments of the invention, the diazabicyclo is present in an amount of 0.5-4.0 wt%, based on the total weight of the absorption liquid. In some embodiments of the present invention, the diazabicyclo may be present in an amount of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 3.0wt%, 4.0wt%, etc., based on the total weight of the absorption liquid. In some preferred embodiments of the invention, the diazabicyclo is present in an amount of 1.0 to 2.0wt%, based on the total weight of the absorption liquid. In some more preferred embodiments of the invention, the diazabicyclo is present in an amount of 1.0 to 1.5wt%, based on the total weight of the absorption liquid.
In some embodiments of the invention, the morpholine is present in an amount of 1.5 to 3.0wt% based on the total weight of the absorption liquid. In some embodiments of the present invention, the morpholine may be present in an amount of 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 4.0wt%, etc., based on the total weight of the absorption liquid. In some preferred embodiments of the invention, the morpholine is present in an amount of 2.0 to 2.5wt% based on the total weight of the absorption liquid.
In some embodiments of the invention, the additives include sodium molybdate, sodium sulfite, and ethylene glycol.
In the present invention, the additive may act as an antioxidant, a corrosion inhibitor, an anti-corrosion agent, and the like. The comprehensive performance of the absorption liquid can be further improved by adding the additive, for example, the absorption liquid has the scale and corrosion inhibition performance.
In some embodiments of the invention, the sodium molybdate is present in an amount of from 0.2 to 0.3 percent by weight based upon the total weight of the absorption liquid.
In other embodiments of the present invention, the sodium sulfite is present in an amount of 0.1 to 0.2wt% based on the total weight of the absorption liquid.
In some embodiments of the invention, the ethylene glycol is present in an amount of 0.3 to 0.5wt% based on the total weight of the absorption liquid. In some embodiments of the present invention, the ethylene glycol may be present in an amount of 0.3wt%, 0.4wt%, 0.5wt%, or the like, based on the total weight of the absorbent. In some preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4 to 0.5wt% based on the total weight of the absorption liquid. In some most preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4wt% based on the total weight of the absorption liquid.
In a second aspect, the present invention provides a method for preparing an absorption liquid according to the first aspect of the present invention, which comprises: the absorption liquid is prepared by mixing triazine, hindered amine and additive with water.
In some embodiments of the invention, the triazine content in the absorption liquid is 10 to 18wt%; the content of the sterically hindered amine is 1 to 5wt%, preferably 2.5 to 4wt%; the content of the additive is 0.1 to 1wt%, preferably 0.6 to 0.8wt%.
In some embodiments of the present invention, the triazine may be present in the absorption liquid in an amount of 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, etc., in weight percent. In some preferred embodiments of the invention, the triazine content in the absorption liquid is 13 to 15wt%.
In some embodiments of the invention, the triazine is 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
In other embodiments of the invention, the sterically hindered amine comprises at least one of diazabicyclo and morpholine, preferably diazabicyclo and morpholine.
The inventors of the present application have found through studies that the absorption amount and absorption rate of H 2 S by an absorption liquid can be increased by adding a sterically hindered amine to the absorption liquid. Further, when the hindered amine includes both diazabicyclo and morpholine, it may be that the absorption performance of the absorption liquid is optimized.
In some embodiments of the invention, the diazabicyclo is present in an amount of 0.5-4.0 wt%, based on the total weight of the absorption liquid. In some embodiments of the present invention, the diazabicyclo may be present in an amount of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 3.0wt%, 4.0wt%, etc., based on the total weight of the absorption liquid. In some preferred embodiments of the invention, the diazabicyclo is present in an amount of 1.0 to 2.0wt%, based on the total weight of the absorption liquid. In some more preferred embodiments of the invention, the diazabicyclo is present in an amount of 1.0 to 1.5wt%, based on the total weight of the absorption liquid.
In some embodiments of the invention, the morpholine is present in an amount of 1.5 to 3.0wt% based on the total weight of the absorption liquid. In some embodiments of the present invention, the morpholine may be present in an amount of 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 4.0wt%, etc., based on the total weight of the absorption liquid. In some preferred embodiments of the invention, the morpholine is present in an amount of 2.0 to 2.5wt% based on the total weight of the absorption liquid.
In some embodiments of the invention, the additives include sodium molybdate, sodium sulfite, and ethylene glycol.
In the present invention, the additive may act as an antioxidant, a corrosion inhibitor, an anti-corrosion agent, and the like. The comprehensive performance of the absorption liquid can be further improved by adding the additive.
In some embodiments of the invention, the sodium molybdate is present in an amount of from 0.2 to 0.3 percent by weight based upon the total weight of the absorption liquid.
In other embodiments of the present invention, the sodium sulfite is present in an amount of 0.1 to 0.2wt% based on the total weight of the absorption liquid.
In some embodiments of the invention, the ethylene glycol is present in an amount of 0.3 to 0.5wt% based on the total weight of the absorption liquid. In some embodiments of the present invention, the ethylene glycol may be present in an amount of 0.3wt%, 0.4wt%, 0.5wt%, or the like, based on the total weight of the absorbent. In some preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4 to 0.5wt% based on the total weight of the absorption liquid. In some most preferred embodiments of the present invention, the ethylene glycol is present in an amount of 0.4wt% based on the total weight of the absorption liquid.
In some embodiments of the invention, the method specifically comprises: weighing the required amounts of triazine, sterically hindered amine and additive; and then mixing the substances with water, and stirring until the substances are dissolved to obtain the absorption liquid.
In a third aspect, the present invention provides the use of an absorption liquid according to the first aspect or an absorption liquid prepared by a method according to the second aspect of the present invention for the removal of H 2 S from a sulphur-containing gas.
In some embodiments of the invention, the volume fraction of H 2 S in the sulfur-containing gas is less than 2.0% based on the total volume of gas.
In other embodiments of the invention, the sour gas comprises at least one of sour natural gas and sour oilfield associated gas.
The beneficial effects of the invention are as follows: compared with the traditional desulfurization absorption liquid, the absorption liquid for removing H 2 S has the advantages of high sulfur removal efficiency, large sulfur capacity and small consumption, and simultaneously has the properties of scale inhibition and corrosion inhibition, thereby achieving the purpose of improving economic benefit.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present invention may be prepared by commercial or conventional methods unless specifically indicated.
The measurement methods used in the following examples were as follows:
Sulfur capacity determination: the feed gas is a mixture of H 2 S and N 2, wherein the volume fraction of H 2 S is 0.15%, the pressure is 2.5MPa, and the temperature is 40 ℃. 300ml of absorption liquid with H 2 S removed is added into a cavity of a high-pressure reaction kettle, and the temperature of the absorption liquid is controlled by the reaction kettle through heat conduction oil in a jacket. The sulfur capacity was measured by bubbling a feed gas containing H 2 S into the autoclave. The flow rate of the raw material gas is 600mL/min in the test, and the zinc acetate solution with the mass fraction of 2% is introduced into the purified gas outlet. The feed gas was started when it was introduced, and the introduction of feed gas was stopped when the zinc acetate solution became significantly white.
And (3) corrosion inhibition performance measurement: the corrosion inhibition performance of the absorption liquid for removing H 2 S is measured by adopting a hanging piece test by referring to a metal material national standard JB/T7901-2001 'metal material laboratory uniform corrosion full immersion test method' and an oil and gas industry standard SY/T5273-2000 'corrosion inhibitor performance evaluation method for oilfield produced water'. The operation steps are as follows: 1) Adding 300mL of high-salt ground mineral water into a reaction kettle chamber, adding 300mL of H 2 S-removed absorption liquid during a comparative test, and adding no blank group; 2) 2 hanging pieces made of the same material are placed in a reaction kettle, so that the hanging pieces are ensured to be completely immersed in a corrosive medium and not to contact the wall surface of the reaction kettle; 3) Filling high-pressure nitrogen (replaced by purified gas standard gas) into the reaction kettle to test pressure; 4) Heating the reaction kettle to 80 ℃ through heat conduction oil, and timing after reaching a preset temperature. After 72h and above, the pressure is relieved, the hanging piece is taken out, the corrosion condition is observed, and special attention is paid to whether cracking and pits exist or not. After the observation is finished, immediately washing with desalted water, brushing with a soft brush or a hard rubber, removing soft corrosion products on the surface layer, finally washing gradually with acetone and absolute ethyl alcohol, drying with cold air, wrapping with filter paper, drying in a dryer for 1h, and weighing to 0.0001g. The hanging piece treatment process comprises the following steps: 1) The hanging piece is prepared by using water-grinding sand paper with the material of 304, the hanging piece is polished by using the water-grinding sand paper with the size of not less than 120 meshes to 2000 meshes, the mesh number of the water-grinding sand paper is reduced from low to high during polishing, rust, marks and burrs are removed, and the surface of the hanging piece is polished to be bright and trace-free; 2) Clamping with forceps, cleaning in petroleum ether or acetone, and removing oily protective film on the surface; 3) Measuring the size by using a vernier caliper; 4) Soaking in absolute ethanol for about 1 minute, taking out, air drying, wrapping with filter paper, standing for drying for 1 hour in the drying period, weighing with a balance to the accuracy of 0.0001g, and storing in a dryer for later use.
And (3) measuring scale inhibition performance: the scale is CaCO 3 type, and the scale inhibition performance test is carried out by referring to GB/T16632-2019 method for measuring the scale inhibition performance of water treatment agent by calcium carbonate deposition. The operation steps are as follows: the preparation water containing a certain amount of bicarbonate and calcium ions and the scale inhibitor are prepared into a test solution, the decomposition of the calcium bicarbonate into calcium carbonate is promoted at 80+/-1 ℃, the concentration of the calcium ions in the test is measured after the balance is achieved, and the greater the concentration of the calcium ions, the better the scale inhibition performance of the scale inhibitor. The scale inhibition performance of the absorption liquid for removing H 2 S is calculated by eta, the numerical value is expressed as percent, and the scale inhibition performance is calculated according to the following formula:
Wherein:
ρ0—preparing a numerical value of the mass concentration of calcium ions in a water sample, in mg/mL;
ρ1—the numerical value of the mass concentration of calcium ions in the formulated water sample without adding the absorption liquid for removing H 2 S, unit mg/mL;
ρ2—the value of the mass concentration of calcium ions in mg/mL in the formulated water sample with the absorption liquid removed from H 2 S.
The specific operation steps are as follows:
① Preparing 1mL of sodium bicarbonate standard solution about 18.3mgHCO 3 - and 1mL of calcium chloride standard solution about 6mgCa 2+;
② Preparing a hydrochloric acid standard titration solution with the concentration of about 0.1mol/L and an ethylenediamine tetraacetic acid (EDTA) standard titration solution with the concentration of about 0.01mol/L, and preparing a borax buffer solution with the pH of about 9, a bromocresol green-methyl red indicator solution and a calcium-carboxylic acid indicator;
③ Preparing a water sample containing calcium ions for the test of adding the absorption liquid for removing H 2 S: 250mL of water is added into a 500 volumetric flask, and a burette is used for adding a certain volume of calcium chloride standard solution, so that the amount of calcium ions is 120mg; adding a certain amount of absorption liquid for removing H 2 S by a pipette, and shaking uniformly; then adding 20mL of borax buffer solution, and shaking uniformly; slowly adding a certain volume of sodium bicarbonate standard solution into a burette to ensure that the amount of bicarbonate ions is 366mg, diluting with water to a scale, and shaking uniformly;
④ Preparing a blank water sample containing calcium ions for experiments: the process is the same as ③ except that no absorption liquid for removing H 2 S is added;
⑤ Respectively placing a calcium ion-containing water sample for test and a calcium ion-containing water sample for blank test containing the H 2 S-removed absorption liquid into two clean conical bottles, immersing the two clean conical bottles into a constant-temperature water bath with the temperature of 80+/-1 ℃ and standing at constant temperature for 10 hours; after the completion, the mixture is dried and filtered by medium-speed quantitative filter paper; after the filtrate cooled, 25mL of filtrate was taken in a conical flask, water was added to about 80mL, 5mL of 200g/L potassium hydroxide solution and about 0.1g of calcium-carboxylic acid indicator were added; and (3) titrating the solution by using an EDTA standard solution until the solution changes from purple red to light blue to obtain an end point, calculating the concentration of calcium ions in the calcium ion-containing water sample for the test and the calcium ion-containing water sample for the blank test containing the absorption liquid for removing H 2 S, and calculating the scale inhibition rate by using the formula.
Example 1
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 85.4g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorbent liquid contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% of diazabicyclo, 2.5wt% of morpholine, 0.2wt% of sodium molybdate, 0.1wt% of sodium sulfite and 0.3wt% of ethylene glycol.
Example 2
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.0g of diazabicyclo, 1.5g of morpholine, 0.2g of sodium molybdate, 0.2g of sodium sulfite and 0.4g of ethylene glycol were added to 86.7g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorption liquid comprises: 10% by weight of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.0% by weight of diazabicyclo, 1.5% by weight of morpholine, 0.2% by weight of sodium molybdate, 0.2% by weight of sodium sulfite and 0.4% by weight of ethylene glycol.
Example 3
15G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 80.4g of water, and after stirring until dissolved, an absorption liquid with H 2 S removed was prepared. The absorbent contained 15wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite, and 0.3wt% ethylene glycol.
Example 4
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 0.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 86.4g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorbent liquid contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 0.5wt% of diazabicyclo, 2.5wt% of morpholine, 0.2wt% of sodium molybdate, 0.1wt% of sodium sulfite and 0.3wt% of ethylene glycol.
Example 5
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.5g of diazabicyclo, 1.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 86.4g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorbent liquid contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% of diazabicyclo, 1.5wt% of morpholine, 0.2wt% of sodium molybdate, 0.1wt% of sodium sulfite and 0.3wt% of ethylene glycol.
Example 6
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.3g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 85.3g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorbent liquid contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% of diazabicyclo, 2.5wt% of morpholine, 0.3wt% of sodium molybdate, 0.1wt% of sodium sulfite and 0.3wt% of ethylene glycol.
Example 7
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.2g of sodium sulfite and 0.3g of ethylene glycol were added to 85.3g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorbent contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.2wt% sodium sulfite, and 0.3wt% ethylene glycol.
Example 8
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 1.5g of diazabicyclo, 2.5g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.4g of ethylene glycol were added to 85.3g of water, and the mixture was stirred until dissolved, thereby obtaining an absorption liquid from which H 2 S was removed. The absorbent contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 1.5wt% diazabicyclo, 2.5wt% morpholine, 0.2wt% sodium molybdate, 0.1wt% sodium sulfite, and 0.4wt% ethylene glycol.
Example 9
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 4g of diazabicyclo, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 85.4g of water, and the mixture was stirred until dissolved, thereby obtaining an absorbent solution from which H 2 S was removed. The absorbent liquid contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine, 4.0wt% of diazabicyclo, 0.2wt% of sodium molybdate, 0.1wt% of sodium sulfite, and 0.3wt% of ethylene glycol.
Example 10
10G of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-S-triazine, 4g of morpholine, 0.2g of sodium molybdate, 0.1g of sodium sulfite and 0.3g of ethylene glycol were added to 85.4g of water, and after stirring until dissolved, an absorption liquid with H 2 S removed was prepared. The absorbent liquid contained 10wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro s-triazine, 4.0wt% of morpholine, 0.2wt% of sodium molybdate, 0.1wt% of sodium sulfite and 0.3wt% of ethylene glycol.
Comparative example 1
13G of 1,3, 5-three (2-hydroxyethyl) -hexahydro S-triazine is added into 87.0g of water, and after stirring until dissolved, an absorption liquid with H 2 S removed is prepared. The absorption liquid contains 13wt% of 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
Test example 1
The absorption solutions obtained in examples 1 to 10 and comparative example 1, from which H 2 S was removed, were subjected to sulfur capacity measurement, corrosion inhibition performance measurement and scale inhibition performance measurement, respectively, and the results are shown in tables 1 to 3, respectively.
TABLE 1 Sulfur Capacity of H 2 S-removed absorption liquid
TABLE 2 Corrosion inhibition Property of absorbent solution for H 2 S removal (hanging piece of Material 304. Test results at 80+ -1deg.C for 72H under pressure of 3.8-4.4 MPa)
Sequence number Before test (g) After the test (g) Corrosion Rate (mm/a)
Comparative example 1 9.1289 9.1286 0.0035
Example 1 9.0146 9.0144 0.0024
Example 2 7.8306 7.8304 0.0026
Example 3 8.1257 8.1255 0.0023
Example 4 8.1725 8.1723 0.0024
Example 5 7.9562 7.9560 0.0021
Example 6 8.3325 8.3323 0.0027
Example 7 8.8765 8.8763 0.0029
Example 8 8.4526 8.4524 0.0023
Example 9 8.1726 8.1724 0.0027
Example 10 8.1733 8.1731 0.0025
TABLE 3 scale inhibition Properties of absorption liquid for H 2 S removal
The results in tables 1 to 3 above show that: compared with the single triazine absorption liquid (comparative example 1), the absorption liquid (examples 1-10) has the advantages of large sulfur capacity, small dosage and scale and corrosion inhibition.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (12)

1. An absorption liquid for removing H 2 S from sulfur-containing gas, which comprises the following components in percentage by weight:
10 to 18wt% of a triazine;
1 to 5wt% of a sterically hindered amine;
0.1 to 1wt% of an additive; and
The balance of water; the hindered amines include diazabicyclo and morpholine;
The content of the diazabicyclo is 0.5-4.0wt% based on the total weight of the absorption liquid; the content of the morpholine is 1.5 to 4.0 weight percent;
The volume fraction of H 2 S in the sulfur-containing gas is less than 2.0% based on the total volume of the gas.
2. The absorption liquid according to claim 1, which comprises the following components in percentage by weight:
13 to 15wt% of triazine;
2.5 to 4wt% of a sterically hindered amine;
0.6 to 0.8wt% of an additive; and
The balance of water.
3. The absorption liquid according to claim 2, wherein the triazine is 1,3, 5-tris (2-hydroxyethyl) -hexahydro-s-triazine.
4. The absorption liquid according to any one of claims 1 to 3, wherein the diazabicyclo is contained in an amount of 1.0 to 2.0wt%, based on the total weight of the absorption liquid; and/or the morpholine content is 2.0-2.5 wt%.
5. The absorbent of claim 4 wherein the diazabicyclo is present in an amount of 1.0 to 1.5wt%, based on the total weight of the absorbent.
6. An absorption liquid according to any one of claims 1-3, wherein the additives comprise sodium molybdate, sodium sulfite and ethylene glycol.
7. The absorption liquid according to claim 6, wherein the content of sodium molybdate is 0.2 to 0.3wt%, based on the total weight of the absorption liquid; and/or the content of sodium sulfite is 0.1-0.2 wt%; and/or the content of the ethylene glycol is 0.3-0.5 wt%.
8. The absorbent according to claim 7, wherein the ethylene glycol is contained in an amount of 0.4 to 0.5wt%.
9. A method for producing the absorbent liquid according to any one of claims 1 to 8, comprising: the absorption liquid is prepared by mixing triazine, hindered amine and additive with water.
10. Use of an absorption liquid according to any one of claims 1-8 or an absorption liquid prepared by a method according to claim 9 for the removal of H 2 S from a sulphur-containing gas.
11. The use according to claim 10, wherein the volume fraction of H 2 S in the sulphur-containing gas is less than 2.0% based on the total volume of gas.
12. The use of claim 11, wherein the sulfur-containing gas comprises at least one of a sulfur-containing natural gas and a sulfur-containing oilfield associated gas.
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