CN116003337A - Triazine desulfurizing agent for crude oil, preparation method and application thereof - Google Patents
Triazine desulfurizing agent for crude oil, preparation method and application thereof Download PDFInfo
- Publication number
- CN116003337A CN116003337A CN202310279460.1A CN202310279460A CN116003337A CN 116003337 A CN116003337 A CN 116003337A CN 202310279460 A CN202310279460 A CN 202310279460A CN 116003337 A CN116003337 A CN 116003337A
- Authority
- CN
- China
- Prior art keywords
- desulfurizing agent
- triazine
- crude oil
- preparation
- semi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 80
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010779 crude oil Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- -1 aldehyde compound Chemical class 0.000 claims abstract description 25
- 239000011265 semifinished product Substances 0.000 claims abstract description 25
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 23
- 230000023556 desulfurization Effects 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 17
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 17
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 17
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 26
- 239000003921 oil Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000005086 pumping Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 3
- HUHGPYXAVBJSJV-UHFFFAOYSA-N 2-[3,5-bis(2-hydroxyethyl)-1,3,5-triazinan-1-yl]ethanol Chemical compound OCCN1CN(CCO)CN(CCO)C1 HUHGPYXAVBJSJV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecanol group Chemical group C(CCCCCCCCCCC)O LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a triazine desulfurizing agent for crude oil, a preparation method and application thereof, and belongs to the field of petrochemical industry. The preparation method comprises the following steps: (1) Adding fatty amine, a catalyst and a solvent into a reaction kettle, and then adding an aldehyde compound to prepare a semi-finished product of the desulfurizing agent; (2) And (3) adding the semi-finished product of the desulfurizing agent and the nonionic surfactant into a reaction kettle for compounding to obtain the triazine desulfurizing agent. The triazine desulfurizer for crude oil provided by the invention is applied to crude oil exploitation, can effectively remove hydrogen sulfide in crude oil exploitation, and has the characteristics of high desulfurization rate, high absorption rate and convenient dosing. Meanwhile, the prepared triazine desulfurizer has oil solubility, can be dissolved in crude oil, and realizes homogeneous desulfurization.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a triazine desulfurizer for crude oil, a preparation method thereof and application of the triazine desulfurizer for crude oil in a crude oil extraction desulfurization process.
Background
Crude oil is extracted along with hydrogen sulfide in the process of extraction, and organic sulfur in the crude oil can be cracked to form hydrogen sulfide at high temperature after the crude oil is subjected to thermal extraction. Sulfide is a gas with malodor, high toxicity and irritation, which not only causes danger to workers, but also causes serious corrosion to oil production pipelines and related equipment because of dissolution of hydrogen sulfide acidic gas, shortens the service life of the pipelines and even causes oil pipe leakage, simultaneously has adverse effect on crude oil transportation and collection, reduces the processability of crude oil and the quality of finished oil, and causes a series of problems such as equipment corrosion, catalyst deactivation and the like because of the existence of sulfide in the crude oil refining process.
The desulfurization methods commonly used at present are physical desulfurization and chemical desulfurization. The physical desulfurization technology has high cost, is not suitable for large-scale application, and the most common chemical agents of the chemical desulfurization technology mainly comprise amines, strong oxides, hydroxides, triazines and the like.
Compared with the conventional alcohol amine desulfurizing agent, the triazine desulfurizing agent has the advantages of high reaction speed with hydrogen sulfide, good selectivity and the like, and plays an irreplaceable role in a plurality of desulfurizing agents. A method for preparing an ionic liquid desulfurizing agent by compounding alcohol amine or s-triazine with an ionic liquid is reported in the patent publication No. CN 101063046 a. The patent with publication number CN 104449810A reports a preparation method of a low-temperature desulfurizing agent in crude oil by adopting a mode of compounding sym-triazine and alcohol amine. The compounding of oxazolidine with s-triazine is reported in the patent publication No. CN 105056710A to be capable of improving the water solubility of the product and the reaction rate and reaction efficiency of the desulfurizing agent and hydrogen sulfide. However, the triazine desulfurizer is used for removing sulfur and then generating pipeline scaling, and the triazine desulfurizer is synthesized by adopting alcohol amine, alcohol amine is generated again after replacement with hydrogen sulfide in the desulfurization process, and alcohol amine and dithiazide continue to react with hydrogen sulfide in multiple steps to form white polysulfide polymer precipitate, and the problems that the triazine desulfurizer is easy to degrade, does not react thoroughly with hydrogen sulfide and has low desulfurization efficiency in crude oil exist.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a triazine desulfurizer for crude oil, a preparation method and application thereof. The triazine desulfurizer for crude oil is applied to crude oil extraction, can effectively remove hydrogen sulfide in crude oil extraction, and has the characteristics of high desulfurization rate, high absorption rate and convenient dosing. Meanwhile, the prepared triazine desulfurizer has oil solubility, can be dissolved in crude oil, and realizes homogeneous desulfurization.
In one aspect, the present invention provides a triazine desulfurizing agent for crude oil, the triazine desulfurizing agent having a compound represented by formula (I):
in formula (I), R is independently selected from CH 3 -（CH 2 ） n Any one of the above, wherein n is an arbitrary integer of 7 to 19. In another aspect, the present invention provides a method for preparing a triazine desulfurizing agent for crude oil, the method comprising:
(1) Adding fatty amine, a catalyst and a solvent into a reaction kettle, and then adding an aldehyde compound to prepare a semi-finished product of the desulfurizing agent;
(2) And (3) adding the semi-finished product of the desulfurizing agent and the nonionic surfactant into a reaction kettle for compounding to obtain the triazine desulfurizing agent.
In a further aspect, the invention provides the use of a triazine desulfurizing agent for crude oil as described above or as prepared by the method described above in a desulfurization process for crude oil recovery.
The beneficial effects of the invention include at least one of the following:
1. the triazine desulfurizer for crude oil has the advantages that nitrogen atoms and carbon atoms on a triazine molecular structure alternately exist, the nitrogen atoms have an electron-withdrawing induction effect, if the nitrogen atoms are protonated, the electrophilic property of the carbon atoms on a six-membered ring is increased, when hydrogen sulfide or other nucleophilic reagents exist, the electrophilicity of the triazine desulfurizer can promote the attack of the nucleophilic reagents, the reaction is rapid, the selectivity is strong, and the efficient desulfurization is shown;
2. the triazine desulfurizer for crude oil is an oil-soluble desulfurizer, reduces the surface tension of the desulfurizer under the action of a nonionic surfactant, improves the permeability of the desulfurizer in the crude oil, further improves the saturated solubility of the desulfurizer in the crude oil, ensures that the crude oil and the desulfurizer can fully contact and react, and improves the desulfurization efficiency;
3. the triazine desulfurizer for crude oil selects alkylamine as a synthetic raw material, and compared with triazine synthesized by alcohol amine, the generated triazine is not easy to scale;
4. the preparation method of the triazine desulfurizer for crude oil has the advantages of simple operation steps, readily available raw materials, easy industrial production and higher desulfurization rate;
5. by adopting the preparation method of the triazine desulfurizer for crude oil, the prepared triazine desulfurizer is widely applied to oil extraction in oil fields, can effectively remove hydrogen sulfide in crude oil, prevents corrosion of equipment and harm to human bodies, and has the characteristics of low toxicity and biodegradability of desulfurization products.
Detailed Description
In order to more clearly illustrate the general inventive concept, a detailed description is given below by way of example.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
In order to more clearly illustrate the general concepts of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. However, it will be apparent to one skilled in the art that the present application may be practiced without one or more of these details. In other instances, some features well known in the art have not been described in order to avoid obscuring the present application.
Unless otherwise specified, reagents in the following examples, such as: dodecyl amine (CAS: 124-22-1), tetradecyl amine (CAS: 2016-42-4), hexadecyl amine (CAS: 143-27-1), ethanol (CAS: 64-17-5), ethylene glycol (CAS: 107-21-1), ethylene glycol monobutyl ether (CAS: 111-76-2), ethylene diamine tetraacetic acid (CAS: 60-00-4), concentrated sulfuric acid (CAS: 7664-93-9), nonylphenol polyoxyethylene ether NP-5 (CAS: 9016-45-9), nonylphenol polyoxyethylene ether NP-7 (CAS: 127087-87-0), nonylphenol polyoxyethylene ether NP-10 (CAS: 2854-09-3), nonylphenol polyoxyethylene ether NP-15 (CAS: 14409-72-4) are commercially available; the purity of the above reagents was analytically pure.
In one exemplary embodiment of the present invention, the preparation method of the triazine desulfurizing agent for crude oil may be realized by the following steps.
(1) Synthesizing a semi-finished product of the desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding fatty amine, a catalyst and a solvent into the dried and clean reaction kettle, stirring and heating to 70 ℃, then adding an aldehyde compound, controlling the temperature in the reaction process to be not more than 90 ℃, and carrying out heat preservation reaction for 4 hours at 90 ℃ after the feeding is completed, thus obtaining the semi-finished product of the desulfurizing agent.
Wherein the aliphatic amine is selected from any one or more of dodecyl amine, dodecyl amine and hexadecyl amine, however, the invention is not limited thereto. Preferably, the fatty amine is dodecanol. The aldehyde compound is selected from any one of 37% formaldehyde solution and paraformaldehyde, however, the present invention is not limited thereto. The catalyst is selected from any one or more of ethylenediamine tetraacetic acid and concentrated sulfuric acid, however, the present invention is not limited thereto. The solvent is selected from any one of ethanol, ethylene glycol monobutyl ether, however, the present invention is not limited thereto. Preferably, the solvent is ethanol. The reaction mole ratio of the fatty amine to the aldehyde compound is 1-1.2: 1. the catalyst accounts for 1-5% of the total mass of the fatty amine and the aldehyde compound according to the mass percentage. The solvent accounts for 5-10% of the total mass of the fatty amine and the aldehyde compound.
When the aldehyde compound is 37% formaldehyde solution, the aldehyde compound is added into the solution in a dropwise manner. When the aldehyde compound is paraformaldehyde, the aldehyde compound is added into the solution in a mode of adding the aldehyde compound in batches.
(2) Synthesis of triazine desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping the semi-finished product of the desulfurizing agent into the dried and cleaned reaction kettle, adding a nonionic surfactant into the reaction kettle, heating to 40 ℃, and stirring for 30min until the state is uniform, thus obtaining the triazine desulfurizing agent.
Wherein the nonionic surfactant is selected from any one or more of nonylphenol polyoxyethylene ether NP-5, nonylphenol polyoxyethylene ether NP-7, nonylphenol polyoxyethylene ether NP-10 and nonylphenol polyoxyethylene ether NP-15, however, the invention is not limited thereto. The reaction mass ratio of the semi-finished product of the desulfurizing agent to the nonionic surfactant is 8-10: 1.
the molecular structure of the triazine desulfurizer prepared by the invention contains 3 nitrogen atoms and 3 carbon atoms, the nitrogen atoms and the carbon atoms alternately exist, the nitrogen atoms have an electron-withdrawing induction effect, if the nitrogen atoms are protonated, the electrophilic property of the carbon atoms on the six-membered ring is increased, and the triazine desulfurizer is easy to react with nucleophilic substances such as hydrogen sulfide and the like, and can react with S in the hydrogen sulfide 2- Irreversible substitution reaction occurs to produce dithiazide. Meanwhile, the triazine desulfurizer is an oil-soluble desulfurizer, and nonpolar groups are introduced, so that the contact area between the triazine desulfurizer and an oil-water interface film is increased, the surface activity is higher, the surface tension can be reduced to a great extent, the triazine desulfurizer is adsorbed at an oil-water interface, the permeability of the triazine desulfurizer in crude oil is improved, the saturated solubility of the triazine desulfurizer in the crude oil is further improved, the crude oil and the triazine desulfurizer can be fully contacted and reacted, and the desulfurization efficiency is improved.
Example 1
The embodiment provides a triazine desulfurizer 1# for crude oil, and the preparation method comprises the following steps:
(1) Synthesizing a semi-finished product of the desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding 190 kg of dodecyl amine, 8 kg of ethylenediamine tetraacetic acid and 22 kg of ethanol into the dried and cleaned reaction kettle, stirring and heating to 70 ℃, then dropwise adding 80 kg of 37% formaldehyde solution, controlling the temperature in the reaction process to be not more than 90 ℃, and carrying out heat preservation reaction at 90 ℃ for 4h after feeding is completed, thus obtaining the semi-finished product of the desulfurizing agent. The reaction equation is as follows:
(2) Synthesis of triazine desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding the 300 kg desulfurizer semi-finished product in the step (1) into the dried and cleaned reaction kettle, adding 33 kg nonylphenol polyoxyethylene ether NP-5 into the reaction kettle, heating to 40 ℃, and stirring for 30min until the state is uniform, thus obtaining the triazine desulfurizer No. 1.
Example 2
The embodiment provides a triazine desulfurizer 2# for crude oil, and the preparation method comprises the following steps:
(1) Synthesizing a semi-finished product of the desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding 220 kg tetramine, 8 kg ethylenediamine tetraacetic acid and 22 kg ethanol into the dried and cleaned reaction kettle, stirring and heating to 70 ℃, then dripping 80 kg of 37% formaldehyde solution, controlling the temperature in the reaction process to be not more than 90 ℃, and carrying out heat preservation reaction at 90 ℃ for 4h after feeding is completed, thus obtaining the semi-finished product of the desulfurizing agent. The reaction equation is as follows:
(2) Synthesis of triazine desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding the semi-finished product of the 330 kg desulfurizing agent in the step (1) into the dried and cleaned reaction kettle, adding 35 kg nonylphenol polyoxyethylene ether NP-5 into the reaction kettle, heating to 40 ℃, and stirring for 30min until the state is uniform, thus obtaining the triazine desulfurizing agent No. 2.
Example 3
The embodiment provides a triazine desulfurizer 3# for crude oil, and the preparation method comprises the following steps:
(1) Synthesizing a semi-finished product of the desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping 270-kg-hexadecylamine and 28-kg-ethanol into the dried and clean reaction kettle, stirring and heating to 70 ℃, then adding 30-kg paraformaldehyde and 3-kg-concentrated sulfuric acid 5 times, adding 6-kg-paraformaldehyde and 0.6-kg-concentrated sulfuric acid each time, controlling the temperature in the reaction process to be not more than 90 ℃, and carrying out heat preservation reaction at 90 ℃ for 4-h after the addition is completed, thus obtaining the semi-finished product of the desulfurizing agent. The reaction equation is as follows:
(2) Synthesis of triazine desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding the semi-finished product of the 331 kg desulfurizing agent in the step (1) into the dried and cleaned reaction kettle, adding 41 kg nonylphenol polyoxyethylene ether NP-7 into the reaction kettle, heating to 40 ℃, and stirring for 30min until the state is uniform, thus obtaining the triazine desulfurizing agent 3#.
Example 4
The embodiment provides a triazine desulfurizer 4# for crude oil, and the preparation method comprises the following steps:
(1) Synthesizing a semi-finished product of the desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping 210 kg of ethylenediamine, 6 kg of ethylenediamine tetraacetic acid and 22 kg of ethylene glycol into the dried and cleaned reaction kettle, stirring and heating to 70 ℃, then adding 30 kg of paraformaldehyde 5 times, adding 6 kg of paraformaldehyde each time, controlling the temperature in the reaction process to be not more than 90 ℃, and carrying out heat preservation reaction at 90 ℃ for 4h after the addition is completed, thus obtaining the semi-finished product of the desulfurizing agent. The reaction equation is as follows:
(2) Synthesis of triazine desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping and adding the semi-finished product of the 268 kg desulfurizing agent in the step (1) into the dried and cleaned reaction kettle, adding 30 kg nonylphenol polyoxyethylene ether NP-10 into the reaction kettle, heating to 40 ℃, and stirring for 30min until the state is uniform, thus obtaining the triazine desulfurizing agent No. 4.
Example 5
The embodiment provides a triazine desulfurizer No. 5 for crude oil, and the preparation method comprises the following steps:
(1) Synthesizing a semi-finished product of the desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping 230 kg tetramine and 20 kg ethylene glycol monobutyl ether into the dried and cleaned reaction kettle, stirring and heating to 70 ℃, then dropwise adding 80 kg of 37% formaldehyde solution, adding 3.5 kg concentrated sulfuric acid after the dropwise adding is finished, controlling the temperature in the reaction process to be not more than 90 ℃, and carrying out heat preservation reaction at 90 ℃ for 4h after the feeding is finished, thus obtaining the semi-finished product of the desulfurizing agent. The reaction equation is as follows:
(2) Synthesis of triazine desulfurizing agent:
cleaning and drying a stainless steel reaction kettle, pumping 333.5 kg desulfurizer semi-finished products in the step (1) into the dried and cleaned reaction kettle, adding 40 kg nonylphenol polyoxyethylene ether NP-15 into the reaction kettle, heating to 40 ℃, and stirring for 30min until the state is uniform, thus obtaining the triazine desulfurizer No. 5.
Test 1
And (3) carrying out indoor desulfurization experiments on the triazine desulfurizing agents 1# to 5# prepared in the embodiments 1-5, and comparing the test results with the on-site desulfurizing agents. The in-situ desulfurizing agent has the structure of 1,3, 5-tri (2-hydroxyethyl) -hexahydro-s-triazine. The specific test method is as follows:
(1) Weigh 1.0 g Na 2 S·9H 2 O, 99.0. 99.0 g deionized water was added to prepare a sodium sulfide solution with a concentration of 1%.
(2) 98% concentrated sulfuric acid of 1.53 and g is weighed into a reagent bottle, and 98.47 g deionized water is added to prepare a dilute sulfuric acid solution with the concentration of 1.5%.
(3) Weighing 6.0 g sodium sulfide solution in the step (1) respectively into 6 500 mL wide-mouth bottles, adding 100 g deionized water, covering a cover capable of placing a detection tube, adding 100 uL triazine desulfurizing agents 1# to 5# and on-site desulfurizing agents into the 6 wide-mouth bottles respectively by using a liquid transfer device, shaking uniformly, adding 0.64 mL dilute sulfuric acid solution in the step (2), quickly covering the cover, putting the bottles into a constant-temperature water bath at 50 ℃, shaking uniformly, reacting for 30min, and simultaneously performing a blank experiment, wherein the concentration of hydrogen sulfide in the blank sample is 600 mg/L.
(4) After 45 min, the concentration of hydrogen sulfide in the wide-mouth bottle is tested by using a hydrogen sulfide detection tube, and the hydrogen sulfide detection tube is sealed with a rubber tube by using an adhesive tape to avoid the entry of external air.
Calculating the desulfurization rate of the sample according to the formula (2):
M0-H in blank sample 2 S measured value, mg/L;
m1-desulfurizing agent-added H 2 S measured value, mg/L;
x-desulfurization percentage%
The desulfurization rate test results are shown in table 1.
As can be seen from Table 1, the triazine desulfurizing agents 1# to 5# provided in examples 1 to 5 have high desulfurizing effects, and all reach the index that the desulfurizing rate required by the site is more than or equal to 90%, wherein the triazine desulfurizing agent 1# has the best effect and reaches the desulfurizing rate of 98.7%, which is higher than that of the site desulfurizing agent.
Test 2
And (3) performing indoor scaling test on the triazine desulfurizing agents 1# to 5# prepared in the embodiments 1-5, and comparing the test results with the field samples. The in-situ desulfurizing agent has the structure of 1,3, 5-tri (2-hydroxyethyl) -hexahydro-s-triazine. The specific test method is as follows:
(1) Weighing 10g of Na 2 S·9H 2 O, 30g of deionized water was added to prepare a 25% sodium sulfide solution.
(2) 10g of 98% concentrated sulfuric acid is weighed into a reagent bottle, and 30g of deionized water is added to prepare a dilute sulfuric acid solution with the concentration of 25%.
(3) The sodium sulfide solution of 12 and g in the step (1) is weighed and added into 6 wide-mouth bottles of 500 and mL, deionized water of about 50 and g is added, the dilute sulfuric acid solution of 2 and mL in the step (2) is added, and a cover is quickly covered, so that hydrogen sulfide gas is obtained.
(4) And respectively weighing triazine desulfurizing agents 1# to 5# and on-site desulfurizing agents 10g to 6 conical flasks of 250 ml, adding 50 ml deionized water for dilution, covering an open-pore bottle stopper, binding a balloon at one end, connecting hydrogen sulfide gas at the other end, continuously introducing the hydrogen sulfide gas, and stopping introducing when the balloon swells to prove that the desulfurizing agents absorb the hydrogen sulfide to be saturated.
The precipitation was observed and the test results are shown in table 2.
As can be seen from Table 2, the triazine desulfurizing agents 1# to 5# provided in examples 1 to 5 have no scale formation during the hydrogen sulfide removal process, while the in-situ desulfurizing agent has scale formation.
Test 3
The triazine desulfurizing agent 1# prepared in the example is applied on site, and the result is compared with the on-site desulfurizing agent. The in-situ desulfurizing agent has the structure of 1,3, 5-tri (2-hydroxyethyl) -hexahydro-s-triazine.
The continuous injection type is adopted for field application, and is added into the produced liquid, and the produced liquid is uniformly injected through a plunger pump. And detecting the content of the sulfur in the detection port by adopting a hydrogen sulfide detector, wherein the content of the sulfur is 1200 ppm when the desulfurizing agent is not added. The test results obtained are shown in Table 3.
When the on-site desulfurizing agent was used, the content of hydrogen sulfide was detected to be 9 ppm, and after the triazine desulfurizing agent 1# prepared in the example was added, the content of hydrogen sulfide was detected to be 2 ppm. From the test data, the triazine desulfurizing agent 1# prepared in the example is superior to the in-situ desulfurizing agent in-situ application.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principles of the present application are intended to be included within the scope of the claims of the present application.
Claims (10)
1. A triazine desulfurizing agent for crude oil, characterized in that the triazine desulfurizing agent has a compound represented by formula (I):
in formula (I), R is independently selected from CH 3 -（CH 2 ） n Any one of the above, wherein n is an arbitrary integer of 7 to 19.
2. The triazine desulfurizing agent for crude oil according to claim 1, wherein R is independently selected from CH 3 -（CH 2 ） n -any one of which n takes on any integer from 11 to 15.
3. A process for the preparation of a triazine desulfurizing agent for crude oil according to claim 1, which comprises:
(1) Adding fatty amine, a catalyst and a solvent into a reaction kettle, and then adding an aldehyde compound to prepare a semi-finished product of the desulfurizing agent;
(2) And (3) adding the semi-finished product of the desulfurizing agent and the nonionic surfactant into a reaction kettle for compounding to obtain the triazine desulfurizing agent.
4. The preparation method according to claim 3, wherein the fatty amine in the step (1) is one or more selected from the group consisting of dodecylamine, dodecylamine and hexadecylamine; the aldehyde compound is selected from any one of 37% formaldehyde aqueous solution and paraformaldehyde; the catalyst is selected from any one or more of ethylenediamine tetraacetic acid and concentrated sulfuric acid; the solvent is selected from any one of ethanol, ethylene glycol and ethylene glycol monobutyl ether.
5. The preparation method of claim 3, wherein the catalyst in the step (1) accounts for 1-5% of the total mass of the fatty amine and the aldehyde compound in percentage by mass.
6. The preparation method of claim 3, wherein the solvent in the step (1) accounts for 5-10% of the total mass of the fatty amine and the aldehyde compound in percentage by mass.
7. The preparation method of claim 3, wherein the reaction molar ratio of the fatty amine to the aldehyde compound in the step (1) is 1 to 1.2:1.
8. the method according to claim 3, wherein the nonionic surfactant in the step (2) is selected from one or more of nonylphenol polyoxyethylene ether NP-5, nonylphenol polyoxyethylene ether NP-7, nonylphenol polyoxyethylene ether NP-10, and nonylphenol polyoxyethylene ether NP-15.
9. The preparation method of claim 3, wherein in the step (2), the reaction mass ratio of the semi-finished desulfurizing agent to the nonionic surfactant is 8-10: 1.
10. use of the triazine desulfurizing agent for crude oil according to any one of claims 1 to 2 or the triazine desulfurizing agent for crude oil produced by the method according to any one of claims 3 to 9 in a desulfurization process for crude oil production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310279460.1A CN116003337A (en) | 2023-03-22 | 2023-03-22 | Triazine desulfurizing agent for crude oil, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310279460.1A CN116003337A (en) | 2023-03-22 | 2023-03-22 | Triazine desulfurizing agent for crude oil, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116003337A true CN116003337A (en) | 2023-04-25 |
Family
ID=86037652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310279460.1A Pending CN116003337A (en) | 2023-03-22 | 2023-03-22 | Triazine desulfurizing agent for crude oil, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116003337A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354453A (en) * | 1993-04-13 | 1994-10-11 | Exxon Chemical Patents Inc. | Removal of H2 S hydrocarbon liquid |
| CN106433835A (en) * | 2016-11-16 | 2017-02-22 | 西安亿道悦达石油科技有限公司 | Oil-gas desulfurizing agent and application |
-
2023
- 2023-03-22 CN CN202310279460.1A patent/CN116003337A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354453A (en) * | 1993-04-13 | 1994-10-11 | Exxon Chemical Patents Inc. | Removal of H2 S hydrocarbon liquid |
| CN106433835A (en) * | 2016-11-16 | 2017-02-22 | 西安亿道悦达石油科技有限公司 | Oil-gas desulfurizing agent and application |
Non-Patent Citations (1)
| Title |
|---|
| 严东寅等: ""一种三嗪类脱硫剂的制备及其性能研究"", 《精细石油化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111265993B (en) | Complex iron desulfurizer | |
| EP0636675A2 (en) | Method of treating sour gas and liquid hydrocarbon streams | |
| JP6412523B2 (en) | Steric hindered amines and related methods | |
| Li et al. | Sugar-based natural deep eutectic solvents as potential absorbents for NH3 capture at elevated temperatures and reduced pressures | |
| CN111822051B (en) | Complex iron desulfurization catalyst | |
| CN107304162B (en) | Gemini surfactant, preparation method and application thereof, oil displacement agent, oil displacement method of oil reservoir, oil stain cleaning agent and oil stain cleaning method | |
| JP6530167B2 (en) | Carbon dioxide chemical absorption liquid and carbon dioxide separation and recovery method | |
| CN112175179A (en) | Preparation method of novel polymerized triazine derivative desulfurizer | |
| CN108864418B (en) | Aging crude oil demulsifier and preparation method thereof | |
| CN116003337A (en) | Triazine desulfurizing agent for crude oil, preparation method and application thereof | |
| CN111517993B (en) | Zwitterionic fluorocarbon surfactant and preparation method thereof | |
| CN109650509A (en) | A kind of oil desulfurization agent | |
| CN107081041B (en) | A kind of hydrogen sulfide gas absorbent and its application | |
| CN116099330A (en) | Method for absorbing hydrogen sulfide gas by using triazine compound | |
| CN109069983B (en) | Premixture for making absorbent for removing acid gases from fluid streams | |
| RU2496853C9 (en) | Hydrogen sulphide neutraliser, and method of its use | |
| CN113321590B (en) | Binuclear quaternary ammonium salt ionic liquid compound and preparation method and application thereof | |
| CN110747002B (en) | Coking corrosion inhibitor | |
| KR101559563B1 (en) | Carbon dioxide absorbent solution comprising guanidine derivatives and method for regenerating the same | |
| CN110734404B (en) | Double-cation ionic liquid with polyethylene glycol chains connected, preparation method and SO 2 Method for trapping gas | |
| US12103872B1 (en) | Polycyclic azide desulfurizer and synthesis method thereof | |
| CN115028826B (en) | Diamino polyether surfactant and preparation method thereof | |
| KR101597204B1 (en) | Aqueous desurfurization compositions for the removal of hydrogen sulfide from gaseous streams | |
| CN113477033B (en) | Self-emulsifiable organic silicon decarbonization solvent | |
| CN113150760A (en) | Novel high-temperature-resistant desulfurizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230425 |
|
| RJ01 | Rejection of invention patent application after publication |