CN113713861A - Composite desulfurization catalyst, desulfurization device using same and desulfurization method - Google Patents

Composite desulfurization catalyst, desulfurization device using same and desulfurization method Download PDF

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CN113713861A
CN113713861A CN202111136561.0A CN202111136561A CN113713861A CN 113713861 A CN113713861 A CN 113713861A CN 202111136561 A CN202111136561 A CN 202111136561A CN 113713861 A CN113713861 A CN 113713861A
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desulfurization
catalyst
weight
gas
sulfur
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范娟娟
杨洪庆
张文婷
郝江洪
李�浩
武玉龙
刘剡
史鑫
辛乐川
王莉
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Xingtai Xuyang Technology Co ltd
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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    • 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
    • B01D53/34—Chemical or biological purification of waste gases
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • 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
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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Abstract

The invention relates to a composite desulfurization catalyst, and a desulfurization device and a desulfurization method using the same. The composite desulfurization catalyst comprises binuclear phthalocyanine cobalt-based sulfonate (PDS) and a complex iron catalyst, wherein the mass ratio of the binuclear phthalocyanine cobalt-based sulfonate (PDS) to iron (Fe) contained in the complex iron catalyst is 0.02-3: 1. The composite desulfurization catalyst has the following advantages: the reaction rate is stable, thereby avoiding the deposition of sulfur in the desulfurizing tower, having good desulfurizing effect and low generation amount of secondary salt.

Description

Composite desulfurization catalyst, desulfurization device using same and desulfurization method
Technical Field
The invention belongs to the field of gas purification, and particularly relates to a composite desulfurization catalyst.
Background
The chemical raw material gas produced by using coal, coke, natural gas and petroleum as raw material contains H with different concentrations2S gas, high concentration H2The existence of S not only pollutes the environment, corrodes the equipment pipeline and influences the quality of chemical products, but also can cause the poisoning and inactivation of the catalyst in the subsequent process production, so H2The technique of S removal is highly appreciated. At present, hydrogen sulfide in coal gas is absorbed mainly by a PDS method, and part of enterprises absorb hydrogen sulfide by a complex iron method.
The PDS method is a wet desulfurization process using sodium carbonate or ammonia as an alkali source and dinuclear phthalocyanine cobalt-based sulfonate (PDS) as a catalyst, and has the basic principle that hydrogen sulfide in coal gas is absorbed into a solution to react with the sodium carbonate or ammonia to generate sodium hydrosulfide or ammonia hydrosulfide, and the catalyst is used as an oxygen carrier to oxidize the sodium hydrosulfide or the ammonia hydrosulfide into elemental sulfur, so that the aim of desulfurization is fulfilled. However, the PDS method has a slow reaction rate and produces a large amount of by-products.
The complex iron method desulfurization is to utilize different ligands to carry out complex coordination on ferric ions to form a complex. The hydrogen sulfide reacts with sodium carbonate in the desulfurization solution to generate sodium hydrosulfide, the sodium hydrosulfide is oxidized into elemental sulfur by utilizing the oxidability of ferric ions, and the ferric ions are reduced into ferrous ions. The ferrous iron ions react with oxygen in the air and then are converted into ferric iron ions for recycling. The disadvantages are that the reaction rate is too fast, the sulfur is generated fast, and the sulfur is gradually attached to the filler due to the current type selection of the desulfurization tower filler, thereby causing the system resistance to rise.
Disclosure of Invention
The invention provides a composite desulfurization catalyst and a preparation method thereof, which improve the problems in the use process of the desulfurization catalyst, and the composite desulfurization catalyst is suitable for removing hydrogen sulfide gas in coke oven gas.
On one hand, the invention provides a composite desulfurization catalyst, which comprises dinuclear phthalocyanine cobalt-based sulfonate (PDS) and a complex iron catalyst, wherein the mass ratio of the dinuclear phthalocyanine cobalt-based sulfonate (PDS) to iron (Fe) contained in the complex iron catalyst is 0.02-3: 1, preferably 0.1-1.2: 1.
In a specific embodiment, the complex iron catalyst comprises: soluble ferric salt, a ferric salt complexing agent, a stabilizer, a sulfur modifier and a corrosion inhibitor.
In a specific embodiment, the complex desulfurization catalyst is in the form of an aqueous solution.
In a specific embodiment, the pH value of the aqueous solution is 8-9.
In a specific embodiment, the soluble ferric salt is one or more selected from ferric chloride, ferric sulfate, ferric nitrate, ferric ammonium salt, ferric sodium ethylene diamine tetraacetate and hydrous ferric oxide.
In a specific embodiment, the iron salt complexing agent is one or more selected from disodium ethylenediaminetetraacetate, sodium citrate, tetrasodium iminodisuccinate, hydroxyethylenediphosphonic acid, nitrilotriacetic acid and hydroxyethylethylenediaminetriacetic acid, in particular disodium ethylenediaminetetraacetate.
In a specific embodiment, the stabilizer is one or two selected from the group consisting of anhydrous glucose, maltose.
In a specific embodiment, the sulfur modifier is one or more selected from sodium polystyrene sulfonate, glycerin, propylene glycol, polyethylene glycol and polyethylene glycol ether, and is especially polyethylene glycol.
In a specific embodiment, the corrosion inhibitor is one or more selected from sodium molybdate, sodium antimonate, silicate, zinc salt, chromate and imidazole, and is especially sodium molybdate.
In a specific embodiment, the composite desulfurization catalyst comprises the following components:
and (2) PDS: 0.1-5 parts by weight; soluble iron salt: 5-15 parts by weight; iron salt complexing agent: 8-24 parts by weight; a stabilizer: 1-10 parts by weight; a sulfur modifier: 0.1-2 parts by weight; corrosion inhibitor: 0.01-1 weight part.
In a specific embodiment, the composite desulfurization catalyst comprises the following components:
and (2) PDS: 0.1-5 parts by weight; iron chloride: 5-15 parts by weight; disodium ethylene diamine tetraacetate: 8-24 parts by weight; anhydrous glucose: 1-10 parts by weight; polyethylene glycol: 0.1-2 parts by weight; sodium molybdate: 0.01-1 weight part.
In a specific embodiment, the composite desulfurization catalyst comprises the following components:
and (2) PDS: 0.5-3 parts by weight; iron chloride: 7-15 parts by weight; disodium ethylene diamine tetraacetate: 12-24 parts by weight; anhydrous glucose: 3-10 parts by weight; polyethylene glycol: 0.5-2 parts by weight; sodium molybdate: 0.4-1 weight portion.
In a specific embodiment, the composite desulfurization catalyst comprises the following components:
water: 1000 parts by weight; and (2) PDS: 0.1-5 parts by weight; soluble iron salt: 5-15 parts by weight; iron salt complexing agent: 8-24 parts by weight; a stabilizer: 1-10 parts by weight; a sulfur modifier: 0.1-2 parts by weight; corrosion inhibitor: 0.01-1 weight part.
In a specific embodiment, the composite desulfurization catalyst comprises the following components:
water: 1000 parts by weight; and (2) PDS: 0.1-5 parts by weight; iron chloride: 5-15 parts by weight; disodium ethylene diamine tetraacetate: 8-24 parts by weight; anhydrous glucose: 1-10 parts by weight; polyethylene glycol: 0.1-2 parts by weight; sodium molybdate: 0.01-1 weight part.
In a specific embodiment, the composite desulfurization catalyst comprises the following components:
water: 1000 parts by weight; and (2) PDS: 0.5-3 parts by weight; iron chloride: 7-15 parts by weight; disodium ethylene diamine tetraacetate: 12-24 parts by weight; anhydrous glucose: 3-10 parts by weight; polyethylene glycol: 0.5-2 parts by weight; sodium molybdate: 0.4-1 weight portion.
In another aspect, the present invention provides a preparation method of the above composite desulfurization catalyst, including:
adding an iron salt complexing agent into water, then adding soluble iron salt, sequentially adding a stabilizer, a sulfur modifier and a corrosion inhibitor, and adding PDS after all substances are uniformly mixed.
In a specific embodiment, the method further comprises the step of adjusting the pH value of the mixture solution obtained by the step to 8-9 by using an alkaline substance.
In a specific embodiment, the alkaline substance may be selected from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, and particularly, the alkaline substance is sodium carbonate.
In another aspect, the invention provides an application of the composite desulfurization catalyst in the desulfurization of coke oven gas or chemical raw material gas.
In still another aspect, the present invention provides a desulfurization apparatus for a gas or chemical feed gas, comprising the following processing units:
the organic sulfur reactor is used for removing organic sulfur in precooled gas or chemical raw gas;
a desulfurization tower connected to the organic sulfur reactor through a pipeline, in which the composite desulfurization catalyst is accommodated, for removing inorganic sulfur (e.g., hydrogen sulfide) from a gas or chemical feed gas;
a reaction tank connected with the desulfurization tower through a pipeline and used for containing desulfurization solution flowing out of the desulfurization tower;
the regenerator is respectively connected with the reaction tank and the desulfurizing tower through pipelines, and is used for regenerating the composite desulfurizing catalyst through injected air, and in the regenerator, the regenerated desulfurizing catalyst overflows from the top of the regenerator and enters the desulfurizing tower for recycling; and
and the foam tank is connected with the regenerator through a pipeline and is used for treating the sulfur floating from the top of the regenerator.
In another aspect, the present invention provides a method for continuously desulfurizing a gas or chemical feed gas by using the above desulfurization apparatus, the method comprising the steps of:
1) organic sulfur removal: organic sulfur in the coal gas or the chemical raw material gas is removed through an organic sulfur reactor;
2) inorganic sulfur removal: the gas or chemical raw material gas from which the organic sulfur is removed enters a desulfurizing tower, and inorganic sulfur (such as hydrogen sulfide) in the gas or chemical raw material gas is removed through treatment of a composite desulfurizing catalyst in the desulfurizing tower;
3) the regeneration and recycling of the catalyst, namely returning the regenerated catalyst to a desulfurizing tower for removing inorganic sulfur, wherein the steps comprise:
the desulfurization solution subjected to the desulfurization process in the desulfurization tower flows from the desulfurization tower into the reaction tank and is sent (for example, by pumping) to the regenerator;
the desulfurization solution flowing into the regenerator is contacted with air in the regenerator for regeneration and then is sent into the desulfurization tower for recycling;
the sulfur floating from the top of the regenerator enters a foam tank for treatment.
Advantageous effects
The inventor considers that the complex iron catalyst has high reaction rate and the PDS has low reaction rate in the desulfurization process, so that the desulfurization reaction speed is moderate by creatively combining the complex iron catalyst and the PDS. In addition, considering the resistance caused by the deposition of the sulfur product in the tower, the moderate reaction speed can prevent the deposition of the sulfur in the tower and separate the sulfur in the subsequent process.
Therefore, the composite desulfurization catalyst provided by the invention has the following excellent effects: the reaction rate is stable, the desulfurization effect is good, the generation amount of secondary salt is low, the color of the generated sulfur is positive, in addition, the corrosion of the desulfurization catalyst to desulfurization equipment is greatly reduced by selecting the corrosion inhibitor, and the pressure drop in long-period operation is stable at a lower level.
Drawings
Fig. 1 is a flow chart of a pilot plant using the hybrid desulfurization catalyst of the present application.
Fig. 2 is a pilot plant side-stream process flow diagram using the hybrid desulfurization catalyst of the present application.
Description of reference numerals:
1: organic sulfur reactor
2: desulfurizing tower
3: reaction tank
4: regenerator
5: foam tank
6: desulfurization liquid pump
6': foam pump
Detailed Description
The effect of the composite desulfurization catalyst of the present invention is demonstrated by the following examples, but the invention is not limited to the following embodiments, wherein the raw materials, equipment and methods used are conventional in the art, unless otherwise specified.
Preparation of example 1
Taking 1kg of water as a solvent, firstly adding 12g of disodium ethylene diamine tetraacetate, fully stirring and dissolving, then adding 7.5g of ferric chloride, after completely dissolving, sequentially adding 3g of anhydrous glucose serving as a stabilizer, 0.75g of polyethylene glycol serving as a sulfur modifier and 0.4g of sodium molybdate serving as a corrosion inhibitor, after all substances are completely mixed uniformly, then adding 3g of PDS, and finally adjusting the pH value of the solution to 8-9 by using an alkaline substance sodium carbonate to prepare the composite desulfurization catalyst.
Preparation of example 2
Taking 1kg of water as a solvent, firstly adding 15.2g of ethylene diamine tetraacetic acid disodium, fully stirring and dissolving, then adding 9.5g of ferric chloride, completely dissolving, then sequentially adding 3.8g of stabilizer anhydrous glucose, 0.95g of sulfur modifier polyethylene glycol and 0.51g of corrosion inhibitor sodium molybdate, completely and uniformly mixing all the substances, then adding 2.4g of PDS, and finally adjusting the pH value of the solution to 8-9 by using an alkaline substance sodium carbonate to prepare the composite desulfurization catalyst.
Preparation of example 3
Taking 1kg of water as a solvent, firstly adding 18.4g of ethylene diamine tetraacetic acid disodium, fully stirring and dissolving, then adding 11.5 g of ferric chloride, after completely dissolving, sequentially adding 4.6g of stabilizer anhydrous glucose, 1.15g of sulfur modifier polyethylene glycol and 0.61g of corrosion inhibitor sodium molybdate, after all substances are completely mixed uniformly, then adding 1.8g of PDS, and finally adjusting the pH value of the solution to 8-9 by using an alkaline substance sodium carbonate to prepare the composite desulfurization catalyst.
Preparation of example 4
Taking 1kg of water as a solvent, firstly adding 21.6g of ethylene diamine tetraacetic acid disodium, fully stirring and dissolving, then adding 13.5g of ferric chloride, completely dissolving, then sequentially adding 5.4g of stabilizer anhydrous glucose, 1.35g of sulfur modifier polyethylene glycol and 0.72g of corrosion inhibitor sodium molybdate, completely and uniformly mixing all the substances, then adding 1.2g of PDS, and finally adjusting the pH value of the solution to 8-9 by using an alkaline substance sodium carbonate to prepare the composite desulfurization catalyst.
Preparation of example 5
Taking 1kg of water as a solvent, firstly adding 24g of ethylene diamine tetraacetic acid disodium, fully stirring and dissolving, then adding 15g of ferric chloride, after completely dissolving, sequentially adding 6g of stabilizer anhydrous glucose, 1.5g of sulfur modifier polyethylene glycol and 0.8g of corrosion inhibitor sodium molybdate, after all the substances are completely mixed uniformly, then adding 0.6g of PDS, and finally adjusting the pH value of the solution to 8-9 by using alkaline substance sodium carbonate to prepare the composite desulfurization catalyst.
The invention adopts a complex iron and PDS compounding mode to form a new desulfurization catalyst, and the optimal compounding ratio is screened out by adjusting the ratio of the complex iron and PDS. In order to further illustrate the desulfurization effect of the present invention, the desulfurization catalysts in the preparation examples were subjected to performance tests.
Example 1: bench test
1. Conditions of the experiment
Experimental gas with hydrogen sulfide concentration of 6000ppm (balance gas is nitrogen)
The experimental gas flow rate is 150ml/min
The pH value of the composite desulfurization catalyst is 8.5-9
2. Procedure of experiment
(1) Primary desulfurization:
the desulfurization catalysts prepared in preparation examples 1 to 5 were diluted 3 times with water to obtain desulfurization solutions, 100ml of the desulfurization solutions was placed in a 250ml round-bottomed flask, 6000ppm of hydrogen sulfide gas was injected into the 250ml round-bottomed flask at a rate of 160ml/min in a bubbling absorption manner, and outlet hydrogen sulfide was detected online by a hydrogen sulfide detector until the outlet hydrogen sulfide could be detected, and the aeration time was recorded. During the test, the pH of the desulfurization solution in the glass container is detected by a pH meter, and the pH of the desulfurization solution is maintained at the initial pH in the test process by a separating funnel mode. At the end of the test, the mass S of saturated and removed hydrogen sulfide per unit volume of the desulfurization catalyst is calculated by the following formula. After the experiment, samples were taken to measure the total iron concentration, the ferric iron concentration and the ferrous iron concentration. The flow chart of the lab evaluation device is shown in FIG. 1.
Calculating the formula:
Figure BDA0003282615040000061
(2) regeneration after desulfurization:
and (3) regenerating the desulfurization solution subjected to primary desulfurization in a bubbling absorption mode by connecting instrument air, and observing the generation of light yellow particles in the flask when the color of the desulfurization solution is recovered to the color before the primary desulfurization, thereby indicating that the diluted desulfurization catalyst is completely regenerated. Stopping introducing instrument air, filtering and separating the regenerated desulfurization solution, wherein light yellow particles on a filter cake are sulfur, and the filtrate is the regenerated desulfurization solution. Sampling and analyzing the total iron concentration, the ferric iron concentration and the ferrous iron concentration of the desulfurized liquid after regeneration.
(3) And (3) desulfurizing the regenerated desulfurization solution again:
and (3) placing 100ml of regenerated desulfurization solution into a 250ml round-bottom flask, injecting 6000ppm hydrogen sulfide gas into the 250ml round-bottom flask in a bubbling absorption mode at the speed of 160ml/min, carrying out online detection on outlet hydrogen sulfide by a hydrogen sulfide detector until the outlet hydrogen sulfide can be detected, and recording the ventilation time. During the test, the pH of the desulfurization solution in the glass container is detected by a pH meter, and the pH of the desulfurization solution is maintained at the initial pH in the test process by a separating funnel mode. After the experiment is finished, the mass of saturated hydrogen sulfide removal of the desulfurization catalyst per unit volume is calculated through the formula. After the experiment, samples were taken to measure the total iron concentration, the ferric iron concentration and the ferrous iron concentration.
3. The experimental results are as follows:
table 1: results of pilot scale experiments
Figure BDA0003282615040000071
From the data in table 1 above, it can be seen that the ratio of the total iron content in the catalyst to PDS gradually increases from example 1 to 5, and from the test results, the higher the ratio of the two is, the better the effect of removing hydrogen sulfide is, and the test data in the table shows that the total iron concentration of the desulfurization solution is not changed much after primary desulfurization and secondary desulfurization, which indicates that the complex iron in the catalyst is relatively stable and no iron ion precipitation occurs.
Example 2: pilot test siding performance evaluation:
2500m of a certain coking plant in Hebei3And evaluating the performance of the catalyst at the desulfurization side line of the coke oven gas. The content of hydrogen sulfide in the coke oven gas is 3-4g/m3The side stream process is shown in FIG. 2. After precooling, the coal gas firstly passes through an organic sulfur reactor 1 to remove organic sulfur, then enters a desulfurizing tower 2, inorganic sulfur (mainly hydrogen sulfide) is removed by using the compound catalyst prepared in the preparation embodiment, the desulfurizing liquid flowing out of the bottom of the desulfurizing tower 2 passes through a reaction tank 3 (namely an intermediate tank) and enters a regenerator 4 through a desulfurizing liquid pump 6, the catalyst is regenerated, the regenerated desulfurizing catalyst overflows from the top of the regenerator 4 and enters the desulfurizing tower 2 for recycling, and the sulfur floating from the top of the regenerator 4 enters a foam tank 5 for treatment and is sent to a filter press through a foam pump 6'.
The catalyst of preparation example 5 was selected for evaluation of hydrogen sulfide removal, amount of by-product formation and system operation pressure, and the test results are shown in tables 2 to 4 below.
Table 2: operating results for hydrogen sulfide removal
Figure BDA0003282615040000081
Table 3: operating results for amount of secondary salt formation
Figure BDA0003282615040000082
Table 4: system operating pressure
Figure BDA0003282615040000083
The results of the operation of the amount of the secondary salt produced by the conventional PDS method and the results of the operation pressure of the system by the conventional complex iron method are shown in tables 5 and 6 below, respectively.
Table 5: operating result of byproduct salt production amount of existing PDS method
Figure BDA0003282615040000091
Table 6: operating pressure results of the existing complex iron method system
Figure BDA0003282615040000092
1. From the long-term operation results of removing hydrogen sulfide in the above table 2, the desulfurization catalyst of the present invention controls the content of hydrogen sulfide after gas desulfurization to be below 20ppm, and meets the desulfurization standard of gas;
2. from the operation results of the byproduct salt production in tables 3 and 5, the byproduct salt production of the catalyst is reduced compared with the byproduct salt production of the existing pure PDS method, so that the amount of waste liquid generated by the catalyst is relatively small under the condition of long-period operation, the pressure of a subsequent salt extraction process is reduced, and the current environment-friendly situation is met.
3. Compared with the system operation pressure result of the existing complex iron method in the table 6, the table 4 shows that the long-period operation pressure of the system is obviously reduced by using the composite type desulfurization catalyst, and the system can be reduced to below 1.5kpa after running for half a year, thereby meeting the control index of the existing desulfurization tower.

Claims (10)

1. A composite desulfurization catalyst comprises binuclear phthalocyanine cobalt-based sulfonate (PDS) and a complex iron catalyst, wherein the mass ratio of the binuclear phthalocyanine cobalt-based sulfonate (PDS) to iron (Fe) contained in the complex iron catalyst is 0.02-3: 1, and preferably 0.1-1.2: 1.
2. The hybrid desulfurization catalyst according to claim 1, wherein the complex iron catalyst comprises: soluble ferric salt, a ferric salt complexing agent, a stabilizer, a sulfur modifier and a corrosion inhibitor.
3. The composite desulfurization catalyst according to claim 1, wherein the composite desulfurization catalyst is in the form of an aqueous solution, preferably, the aqueous solution has a pH value of 8 to 9.
4. The composite desulfurization catalyst according to claim 2,
the soluble ferric salt is one or more selected from ferric chloride, ferric sulfate, ferric nitrate, ferric ammonium salt, ethylene diamine tetraacetic acid ferric sodium salt and hydrous ferric oxide, and is particularly ferric chloride;
the iron salt complexing agent is one or more selected from disodium ethylene diamine tetraacetate, sodium citrate, tetrasodium iminodisuccinate, hydroxyethylidene diphosphonic acid, nitrilotriacetic acid and hydroxyethylethylenediaminetriacetic acid, and is especially disodium ethylene diamine tetraacetate;
the stabilizer is one or two of anhydrous glucose and maltose, and is especially anhydrous glucose;
the sulfur modifier is one or more selected from sodium polystyrene sulfonate, glycerol, propylene glycol, polyethylene glycol and polyethylene glycol ether, particularly polyethylene glycol;
the corrosion inhibitor is one or more selected from sodium molybdate, sodium antimonate, silicate, zinc salt, chromate and imidazole, and is particularly sodium molybdate.
5. The composite type desulfurization catalyst according to any one of claims 1 to 4,
the compound desulfurization catalyst comprises the following components:
and (2) PDS: 0.1-5 parts by weight; soluble iron salt: 5-15 parts by weight; iron salt complexing agent: 8-24 parts by weight; a stabilizer: 1-10 parts by weight; a sulfur modifier: 0.1-2 parts by weight; corrosion inhibitor: 0.01-1 weight part;
when the composite desulfurization catalyst is in the form of an aqueous solution,
the compound desulfurization catalyst comprises the following components:
water: 1000 parts by weight; and (2) PDS: 0.1-5 parts by weight; soluble iron salt: 5-15 parts by weight; iron salt complexing agent: 8-24 parts by weight; a stabilizer: 1-10 parts by weight; a sulfur modifier: 0.1-2 parts by weight; corrosion inhibitor: 0.01-1 weight part.
6. A method for producing a composite type desulfurization catalyst according to any one of claims 1 to 5, comprising:
adding an iron salt complexing agent into water, then adding soluble iron salt, sequentially adding a stabilizer, a sulfur modifier and a corrosion inhibitor, and adding PDS after all substances are uniformly mixed to obtain a solution.
7. The method according to claim 6, further comprising adjusting the pH value of the obtained solution to 8-9 by using alkaline substances, preferably, the alkaline substances are selected from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, and particularly, the alkaline substances are sodium carbonate.
8. The use of the composite desulfurization catalyst of any one of claims 1 to 5 in the desulfurization of coke oven gas or chemical feed gas.
9. A desulfurization unit for a gas or chemical feed gas, comprising the following treatment units:
the organic sulfur reactor is used for removing organic sulfur in precooled gas or chemical raw gas;
a desulfurization tower connected to the organic sulfur reactor through a pipeline, in which the composite desulfurization catalyst according to any one of claims 1 to 5 is accommodated, for removing inorganic sulfur from a gas or chemical feed gas;
a reaction tank connected with the desulfurization tower through a pipeline and used for containing desulfurization solution flowing out of the desulfurization tower;
the regenerator is respectively connected with the reaction tank and the desulfurizing tower through pipelines, and is used for regenerating the composite desulfurizing catalyst through injected air, and in the regenerator, the regenerated desulfurizing catalyst overflows from the top of the regenerator and enters the desulfurizing tower for recycling; and
and the foam tank is connected with the regenerator through a pipeline and is used for treating the sulfur floating from the top of the regenerator.
10. A method for continuously desulfurizing a gas or chemical feed gas using the desulfurization unit of claim 9, the method comprising the steps of:
1) organic sulfur removal: organic sulfur in the coal gas or the chemical raw material gas is removed through an organic sulfur reactor;
2) inorganic sulfur removal: the gas or chemical raw material gas from which the organic sulfur is removed enters a desulfurizing tower, and inorganic sulfur in the gas or chemical raw material gas is removed through treatment of the composite desulfurizing catalyst in the desulfurizing tower;
3) the regeneration and recycling of the catalyst, namely the catalyst is returned to the desulfurization tower for removing inorganic sulfur after being regenerated, and the steps further comprise:
the desulfurization solution that has undergone the desulfurization process in the desulfurization tower flows from the desulfurization tower into the reaction tank and is sent into the regenerator;
the desulfurization solution flowing into the regenerator is contacted with air in the regenerator for regeneration and then is sent into the desulfurization tower for recycling;
the sulfur floating from the top of the regenerator enters a foam tank for treatment.
CN202111136561.0A 2021-09-27 2021-09-27 Composite desulfurization catalyst, desulfurization device using same and desulfurization method Pending CN113713861A (en)

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