A highly efficient total sulfur removal agent for oil fields

Abstract

The invention belongs to the technical field of desulfurization in oil and gas fields, and specifically discloses an efficient total sulfur removal agent for oil fields. The total sulfur removal agent of the invention is prepared from the following raw materials: 22%-24% of diethylene glycol monobutyl ether, 2,2 ’ ‑Oxydiethanol, reaction products with ammonia and residues of morpholine derivatives 30%‑33%, paraformaldehyde 18%‑21%, 3,3 ’ ‑methylenebis(5‑methyloxazoline) 14%‑16%, bis‑2‑methoxyethylazodicarboxylate 7%‑8%, 3‑methylpyridine 2%‑3%, propylene glycol block polyether 1%, the entire production process route has a high yield, and the obtained product has excellent and stable performance in removing sulfides in oil wells; the quality of the product meets the quality standards.

Description

Technical Field

[0001] The invention belongs to the technical field of desulfurization in oil and gas fields, and in particular relates to an efficient total sulfur removal agent for oil fields. Background Art

[0002] There are many kinds of harmful sulfides produced in oil and gas fields, mainly hydrogen sulfide, chain sulfides, cyclic sulfides, mercaptans, etc. Most of these sulfides are very corrosive to equipment and harmful to human health, especially hydrogen sulfide. Therefore, desulfurizers are needed in the process of oil field exploitation and gathering and transportation. There is a big problem with the existing desulfurizers on the market: due to solubility and dispersibility, most desulfurizers can only treat sulfides in one of the water phase and the oil phase, and different sulfide removal mechanisms are different. Therefore, most desulfurizers can only treat a narrow range of sulfides, and even many can only treat a single type of sulfide. At present, there is a lack of desulfurizers on the market that can simultaneously treat multiple sulfides such as hydrogen sulfide, chain sulfides, cyclic sulfides, mercaptans, etc. In oil wells, it is often necessary to use a variety of different desulfurizers to remove total sulfur. Summary of the invention

[0003] In view of the deficiencies in the above-mentioned prior art, the present invention aims to provide an efficient total sulfur removal agent for oil fields and its preparation method and application. The total sulfur removal agent developed by the present invention has good desulfurization effect in both water-based and oil-based systems and has an efficient desulfurization effect of removing various sulfides such as hydrogen sulfide, chain sulfides, cyclic sulfides, and mercaptans. The use of this total sulfur removal agent can significantly reduce the total sulfur in oil and gas wells.

[0004] A major innovation of the present invention is that we have selected a unique raw material, the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues. The product of its reaction with paraformaldehyde is a special substance with strong oxidizing properties, which has good scavenging properties for chain thioethers and cyclic thioethers, and also has moderate scavenging properties for hydrogen sulfide. Moreover, this reaction product has a certain dispersibility in oil on the basis of being soluble in water, so that the product has the performance basis for removing various sulfides. When the mass ratio of paraformaldehyde to the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues is 53:100, the reaction is complete. Paraformaldehyde itself has the ability to remove hydrogen sulfide. In order to make the system of the present invention more capable of removing hydrogen sulfide and to improve the usability of the product in the oil phase, we actually increase the proportion of paraformaldehyde so that most of the paraformaldehyde in the system participates in the reaction, and a small part of unreacted paraformaldehyde exists as one of the components for removing hydrogen sulfide. In order to ensure that the product has good hydrogen sulfide and mercaptan removal performance in both oil phase and water phase, on the basis of ensuring compatibility, we selected 3,3'-methylenebis(5-methyloxazoline) as the main component for hydrogen sulfide removal. 3,3'-methylenebis(5-methyloxazoline) has excellent hydrogen sulfide removal performance and certain scavenging properties for mercaptans. It is soluble in oil and has a certain solubility in water. Its solubility in water can be further improved by using alcohol ethers as solubilizers. Therefore, we selected diethylene glycol monobutyl ether as the main solvent and bis-2-methoxyethyl azodicarboxylate as the main component for mercaptan removal. At the same time, bis-2-methoxyethyl azodicarboxylate also has a certain effect on hydrogen sulfide removal. 3-Methylpyridine is used as a corrosion inhibition component to protect oilfield pipelines and equipment. Propylene glycol block polyether is used as a defoaming component to provide auxiliary effect for desulfurization. Because we have controlled the proportions of each component just right, we finally obtained a system-stable total sulfur removal agent product, which is soluble in water and has good dispersibility in oil-based systems, and can effectively remove a variety of sulfides.

[0005] The present invention provides an efficient total sulfur removal agent for oil fields, which can be well used in water-based and oil-based systems. It has multiple advantages: wide sulfur removal, can effectively remove hydrogen sulfide, mercaptan, chain sulfide, cyclic sulfide and other major toxic sulfides in oil fields; good safety protection, on the basis of reducing various sulfides to a very low or even zero safety value range, this product can also inhibit the corrosion of sulfides on oil field equipment and pipelines, and can also ensure the health and safety of oil field workers. It can be said that only using this total sulfur removal agent can basically meet all the desulfurization needs of many oil wells.

[0006] In order to achieve the above object, the present invention adopts the following technical scheme:

[0007] One of the technical solutions is an efficient total sulfur removal agent for oil fields, comprising a product of polymerization of a reaction product of paraformaldehyde with a reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (53-70):100 (referred to as polymer EAMR) and diethylene glycol monobutyl ether, wherein the mass ratio of the reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue to diethylene glycol monobutyl ether is (52-55):(16-18), preferably 54:17. Preferably, the polymerization reaction temperature is 60-65°C, and the reaction time is 3-4h.

[0008] When the mass ratio of the reaction product of paraformaldehyde with 2,2'-oxydiethanol with ammonia and morpholine derivative residues is 53:100, the reaction is complete, and the total sulfur removal agent is used as a desulfurizer for chain sulfides and cyclic sulfides in a water-based and / or oil-based system; when there is an excess of paraformaldehyde in the reaction system (the mass ratio exceeds 53:100), the total sulfur removal agent is used as a desulfurizer for hydrogen sulfide, chain sulfides and cyclic sulfides in a water-based and / or oil-based system.

[0009] Technical solution 2, an efficient total sulfur removal agent for oil fields, comprising a product of a polymerization reaction of a reaction product of paraformaldehyde with 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (54.5-70):100, preferably a mass ratio of (54.5-65):100 (referred to as polymer EAMR), 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate and diethylene glycol Monobutyl ether, wherein the mass ratio of paraformaldehyde, the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate and diethylene glycol monobutyl ether is (18-21):(30-33):(14-16):(7-8):(22-24), preferably (18-21):(30-33):15:7:23. Preferably, the polymerization reaction is carried out at a temperature of 60-65°C and a reaction time of 3-4h.

[0010] The total sulfur removal agent, and its preparation method comprises the following steps:

[0011] Step 1: Add the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues into a reaction kettle containing diethylene glycol monobutyl ether, stir evenly, then slowly add paraformaldehyde, control the temperature at 60-65°C to carry out polymerization reaction for 3-4h, until all the solids in the system are dissolved;

[0012] Step 2: Heat the reactor to 75-80°C, then add bis-2-methoxyethyl azodicarboxylate into the reactor, stir until it is dissolved, and cool to 39-42°C;

[0013] Step 3: Add 3,3'-methylenebis(5-methyloxazoline) into the reaction kettle, stir until it is dissolved, and then cool to room temperature to obtain a light yellow uniform transparent liquid, which is the efficient total sulfur remover for oil fields.

[0014] The total sulfur removal agent is used as a desulfurizer for hydrogen sulfide, chain sulfides, cyclic sulfides and mercaptans in a water-based and / or oil-based system.

[0015] The third technical solution is an efficient total sulfur removal agent for oil fields, comprising a product of a polymerization reaction of a reaction product of paraformaldehyde and 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (54.5-70):100, preferably a mass ratio of (54.5-65):100 (referred to as polymer EAMR), 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether, wherein paraformaldehyde, 2,2'- The mass ratio of the reaction product of oxydiethanol with ammonia and morpholine derivative residue, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine, and propylene glycol block polyether is (18-21):(30-33):(14-16):(7-8):(22-24):(2-3):1, preferably (18-21):(30-33):15:7:23:3:1, and more preferably 20:31:15:7:23:3:1. Preferably, the polymerization temperature is 60-65°C and the reaction time is 3-4h.

[0016] Preferably, an efficient total sulfur removal agent for oil fields is composed of the following components: a product of the polymerization reaction of paraformaldehyde with 2,2'-oxydiethanol and ammonia and morpholine derivative residues in a mass ratio of (54.5-70):100, preferably in a mass ratio of (54.5-65):100 (referred to as polymer EAMR), 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether, wherein paraformaldehyde, 2,2 The mass ratio of the reaction product of '-oxydiethanol with ammonia and a morpholine derivative residue, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine, and propylene glycol block polyether is (18-21):(30-33):(14-16):(7-8):(22-24):(2-3):1, preferably (18-21):(30-33):15:7:23:3:1, and more preferably 20:31:15:7:23:3:1.

[0017] The preparation method of the highly efficient total sulfur removal agent for oil fields comprises the following steps:

[0018] Step 1: Add the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues into a reaction kettle containing diethylene glycol monobutyl ether, stir evenly, then slowly add paraformaldehyde, control the temperature at 60-65°C to carry out polymerization reaction for 3-4h, until all the solids in the system are dissolved;

[0019] Step 2: Heat the reactor to 75-80°C, then add bis-2-methoxyethyl azodicarboxylate into the reactor, stir until it is dissolved, and cool to 39-42°C;

[0020] Step 3: Add 3,3'-methylenebis(5-methyloxazoline) to the reactor, stir until it dissolves, then add 3-methylpyridine and propylene glycol block polyether, stir, and then cool to room temperature to obtain a light yellow uniform transparent liquid, which is the efficient total sulfur remover for oil fields.

[0021] The total sulfur removal agent is used as a desulfurizer for hydrogen sulfide, chain sulfide, cyclic sulfide and mercaptan in water-based and / or oil-based systems. The suitable temperature is 2 to 96° C., preferably 30 to 40° C. The addition amount of the total sulfur removal agent is 5000±20ppm.

[0022] In the technical solution adopted by the present invention, the paraformaldehyde is a polymer synthesized with formaldehyde as a monomer, has a molecular weight of 360, and is commonly used in the manufacture of synthetic resins.

[0023] In the technical solution adopted by the present invention, the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residue is an organic compound formed by the reaction of three components, and the molecular formula is C8H 22 N2O4 is easily soluble in water and ethanol. It is not used as a desulfurization component in the prior art. The inventors found that it has a certain effect of removing hydrogen sulfide, but the effect of removing chain sulfides and cyclic sulfides is not strong (less than 50%); the reaction product of 2,2'-oxydiethanol and ammonia and morpholine derivative residues has enhanced oxidizability after reacting with polyformaldehyde, and the effect of removing chain sulfides and cyclic sulfides is greatly improved (removal rate is above 90%).

[0024] In the technical solution adopted by the present invention, the bis-2-methoxyethyl azodicarboxylate is also known as methyl di-2-methoxyethyl azodicarboxylate, and its molecular formula is C8H 14 N2O6 is mainly used to remove mercaptans, hydrogen sulfide, etc.

[0025] In the technical solution adopted by the present invention, the 3,3'-methylenebis(5-methyloxazoline) is an oil-soluble organic substance, which also has a certain solubility in water and can be used as a bactericide and desulfurizer.

[0026] In the technical solution adopted by the present invention, the diethylene glycol monobutyl ether is easily soluble in water and lower alcohols, has high dilution with petroleum hydrocarbons and also has good dispersibility in the oil phase, and is often used as a solvent.

[0027] In the technical solution adopted by the present invention, the 3-methylpyridine, also known as β-methylpyridine, is commonly used as a solvent and has a corrosion inhibition effect.

[0028] In the technical solution adopted by the present invention, the average molecular weight of the propylene glycol block polyether is 1800-2100, and the viscosity at 20°C is 250-300 cPs. Preferably, it is propylene glycol block polyether L61, which has an average molecular weight of 2000 and a viscosity at 20°C of 285 cPs.

[0029] Compared with the existing oil and gas field desulfurizer, the advantages and beneficial effects of the present invention are:

[0030] The total sulfur removal agent of the present invention is used to remove various sulfides such as hydrogen sulfide, mercaptan, chain sulfide, cyclic sulfide, etc. in the process of oil and gas well production. It can be effectively used in both water phase and oil phase, and can effectively remove various sulfides with high content and high toxicity in oil fields, and reduce the total sulfur to within the safety threshold value range. The product has stable performance and is not easy to decompose; it has good safety protection. On the basis of reducing various sulfides to a very low or even zero safety value range, this product can also inhibit the corrosion of sulfides to oil field equipment and pipelines, and can also ensure the health and safety of oil field workers. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0032] Example 1: A method for preparing an efficient total sulfur removal agent for oil fields

[0033] The total sulfur removal agent for oil fields is made from the following raw materials: 23 kg of diethylene glycol monobutyl ether, 33 kg of the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues, 18 kg of polyformaldehyde (molecular weight 360), 15 kg of 3,3'-methylenebis(5-methyloxazoline), 7 kg of bis-2-methoxyethylazodicarboxylate, 3 kg of 3-methylpyridine, and 11 kg of propylene glycol block polyether L6. The total amount of the above raw materials is 100 kg.

[0034] Obtained as follows:

[0035] Weigh the raw materials according to the ratio, add 23kg of diethylene glycol monobutyl ether into the reactor, and then add 33kg The reaction product of 2,2'-oxydiethanol and ammonia and morpholine derivative residues is stirred at a speed of 90r / min, and then 18kg of polyformaldehyde is slowly added, while circulating water is turned on to cool down to control the temperature at 60-65℃. After all the raw materials are added, the temperature is kept at 60-65℃ for 3 hours. After completion, samples are taken for inspection. If undissolved white solid is found in the sample, continue stirring for 0.5h and then take samples. This is repeated until all the solids in the system are dissolved. The total reaction time does not exceed 4 hours; the reactor is heated to 75-80℃, and then 7kg of bis-2-methoxyethyl azodicarboxylate is added to the reactor, and stirring is started at a speed of 200r / min. After 0.5h, cooling is started. When the temperature drops to 39-42℃, the temperature is maintained, and the speed is adjusted to 80r / min and stirring is continued for 1h; continue to stir at a temperature of 39-42℃ and a speed of 80r / min, add 15kg 3,3'-methylenebis(5-methyloxazoline) was added and stirred for 0.5h, then the speed was adjusted to 60r / min, 3kg 3-methylpyridine and 1kg propylene glycol block polyether L61 were added successively and stirred for 1.5h, then allowed to stand and cool to obtain a light yellow uniform transparent liquid, which was the efficient total sulfur remover for oil fields.

[0036] Test method for finished product of total sulfur removal agent

[0037] In oil fields, the contents of methyl mercaptan, dimethyl sulfide, and thiophene are relatively high and highly harmful, so they represent mercaptan, chain sulfide, and cyclic sulfide for desulfurization performance testing. In addition, considering that the number of carbon atoms in methyl mercaptan, dimethyl sulfide, and thiophene molecules is too small and the molecular structure is simple, n-heptyl mercaptan, dibutyl sulfide, and cyclohexyl sulfide are selected as similar controls for testing. Considering the solubility issue, hydrogen sulfide is soluble in both water and oil, while methyl mercaptan, n-heptyl mercaptan, and dimethyl sulfide are soluble in oil and slightly soluble in water, while thiophene, cyclohexyl sulfide, and dibutyl sulfide are soluble in oil but difficult to dissolve in water. Therefore, hydrogen sulfide, methyl mercaptan, n-heptyl mercaptan, and dimethyl sulfide are tested for desulfurization in both water and oil phases, while thiophene, cyclohexyl sulfide, and dibutyl sulfide are only tested for desulfurization in the oil phase. In this test, oilfield simulated water is used to represent the water phase system in the oilfield, and the prepared oil-based drilling fluid is used to represent the oil phase system in the oilfield. Each embodiment is tested according to the following method:

[0038] 1. Water phase desulfurization test

[0039] (1) Preparation of simulated oilfield water

[0040] Take 50g NaCl, 2g MgCl2·6H2O, 6g Na2SO4, and 4g CaCl2, add distilled water and stir to prepare 950ml of mixed solution. Then weigh 0.4g NaHCO3, dissolve it in a small amount of distilled water, and then pour it into the above 950ml mixed solution. Then add distilled water and stir to prepare 1L of mixed solution, which is oilfield simulated water. Prepare several portions of oilfield simulated water in this way.

[0041] (2) Desulfurization test of oilfield simulated water system

[0042] Under the temperature of 35℃±1℃, a certain amount of hydrogen sulfide, methyl mercaptan, n-heptyl mercaptan, and dimethyl sulfide were introduced into each portion of oilfield simulated water (1L) at different time points and the concentration of the above sulfides in the oilfield simulated water system was measured with corresponding instruments, and then 5000±20ppm of the total sulfur removal agent sample was added, stirred at a speed of 200r / min for 1.0h and then allowed to stand for 1.0h, and finally the concentration of the remaining corresponding sulfides in each portion of the oilfield simulated water system was tested. (The content of hydrogen sulfide was detected by a hydrogen sulfide analyzer, methyl mercaptan was detected by a methyl mercaptan analyzer, and n-heptyl mercaptan and dimethyl sulfide were detected by a liquid chromatography analyzer.)

[0043] 2. Oil phase desulfurization test

[0044] (1) Preparation of oil-based drilling fluid

[0045] Take 850g 0# diesel, 10g organic soil, 10g quicklime, 30g Span 60 (as emulsifier) ​​and 100g 30wt% calcium chloride solution, mix them and stir them evenly to obtain oil-based drilling fluid. Several portions of oil-based drilling fluid are prepared in this way.

[0046] (2) Basic steps of oil-based drilling fluid desulfurization test

[0047] Under the temperature condition of 35℃±1℃, take several portions of the above-prepared oil-based drilling fluid, and introduce a certain amount of hydrogen sulfide, methyl mercaptan, dimethyl sulfide, thiophene, n-heptyl mercaptan, dibutyl sulfide, and cyclohexyl sulfide into each portion of the oil-based drilling fluid (1kg) at different time periods, and use corresponding instruments to measure the concentration of the above various sulfides in the oil-based drilling fluid system, then add 5000±20ppm of the total sulfur removal agent sample, stir at a speed of 200r / min for 1.0h, and then stand for 1.0h, and finally test the concentration of the corresponding sulfide remaining in each portion of the oil-based drilling fluid. (The content of hydrogen sulfide is detected by a hydrogen sulfide detector, methyl mercaptan is detected by a methyl mercaptan detector, and dimethyl sulfide, thiophene, n-heptyl mercaptan, dibutyl sulfide, and cyclohexyl sulfide are detected by a liquid chromatography analyzer.)

[0048] The desulfurization test results of the finished total desulfurizer for oil field prepared in Example 1 in water phase and oil phase system (each group of experiments was repeated 2 times) are shown in the following Table 1:

[0049] Table 1

[0050]

[0051] Example 2: A method for preparing an efficient total sulfur removal agent for oil fields

[0052] The total sulfur removal agent for oil fields is made from the following raw materials: 23 kg of diethylene glycol monobutyl ether, 30 kg of the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues, 21 kg of polyformaldehyde (molecular weight 360), 15 kg of 3,3'-methylenebis(5-methyloxazoline), 7 kg of bis-2-methoxyethylazodicarboxylate, 3 kg of 3-methylpyridine, and 11 kg of propylene glycol block polyether L6. The total amount of the above raw materials is 100 kg.

[0053] The specific preparation method of the total sulfur removal agent for oil fields is the same as that of Example 1 except for the difference in the mass of the components.

[0054] The desulfurization test results of the finished total desulfurizer for oil field prepared in Example 2 in the water phase and oil phase system (each group of experiments was repeated 2 times) are shown in the following Table 2:

[0055] Table 2

[0056]

[0057]

[0058] Example 3: A method for preparing an efficient total sulfur removal agent for oil fields

[0059] The total sulfur removal agent for oil fields is made from the following raw materials: 23 kg of diethylene glycol monobutyl ether, 31 kg of the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues, 20 kg of polyformaldehyde (molecular weight 360), 15 kg of 3,3'-methylenebis(5-methyloxazoline), 7 kg of bis-2-methoxyethylazodicarboxylate, 3 kg of 3-methylpyridine, and 11 kg of propylene glycol block polyether L6. The total amount of the above raw materials is 100 kg.

[0060] The specific preparation method of the total sulfur removal agent for oil fields is the same as that of Example 1 except for the difference in the mass of the components.

[0061] The desulfurization test results of the finished total desulfurizer for oil field prepared in Example 3 in the water phase and oil phase system (each group of experiments was repeated 2 times) are shown in Table 3 below:

[0062] Table 3

[0063]

[0064]

[0065] Example 4: A method for preparing an efficient total sulfur removal agent for oil fields

[0066] The total sulfur removal agent for oil fields is prepared from the following raw materials: 17 kg of diethylene glycol monobutyl ether, 54 kg of a reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue, and 29 kg of polyformaldehyde (molecular weight 360), the total of which is 100 kg.

[0067] The method is as follows: the raw materials are weighed according to the ratio, 17 kg of diethylene glycol monobutyl ether is first added into the reactor, and then 54 kg of the reaction product of 2,2'-oxydiethanol and ammonia and morpholine derivative residues are added, stirring is started at a speed of 90 r / min, and then 29 kg of polyformaldehyde is slowly added, while circulating water is turned on to cool the temperature to 60-65°C for polymerization reaction for 3-4 hours, until all the solids in the system are dissolved, and then it is allowed to stand and cool to obtain a light yellow uniform transparent liquid, which is the efficient total sulfur remover for oil fields.

[0068] The desulfurization test results of the finished total desulfurizer for oil field prepared in Example 4 in the water phase and oil phase system (each group of experiments was repeated 2 times) are shown in the following Table 4:

[0069] Table 4

[0070]

[0071] Note: In this embodiment, the amount of the reaction product of the raw material 2,2'-oxydiethanol and ammonia and morpholine derivative residues used in the total sulfur removal agent for oil fields is approximately 1.8 times that of Examples 1 to 3. Therefore, in the sulfur removal test, the amount of cyclic sulfide and chain sulfide to be treated is also increased to about 1.8 times that of Examples 1 to 3, and the amount of hydrogen sulfide and mercaptan to be treated is equivalent to that of Examples 1 to 3.

[0072] Example 5: A method for preparing an efficient total sulfur removal agent for oil fields

[0073] The total sulfur removal agent for oil fields is prepared from the following raw materials: 23 kg of diethylene glycol monobutyl ether, 31 kg of the reaction product of 2,2'-oxydiethanol and ammonia and morpholine derivative residues, 20 kg of polyformaldehyde (molecular weight 360), 15 kg of 3,3'-methylenebis(5-methyloxazoline), and 7 kg of bis-2-methoxyethyl azodicarboxylate, with the total of the above raw materials being 96 kg. Compared with Example 3, 3-methylpyridine and propylene glycol block polyether L61 are not added.

[0074] Obtained as follows:

[0075] Weigh the raw materials according to the ratio, add 23kg of diethylene glycol monobutyl ether into the reactor, and then add 31kg The reaction product of 2,2'-oxydiethanol and ammonia and morpholine derivative residues is stirred at a speed of 90r / min, and then 20kg of polyformaldehyde is slowly added, while circulating water is turned on to cool down to control the temperature at 60-65℃. After all the raw materials are added, the temperature is continued to be kept at 60-65℃ for 3 hours. After completion, samples are taken for inspection. If undissolved white solids are found in the sample, continue stirring for 0.5h and then take samples. This is repeated until all the solids in the system are dissolved. The total reaction time does not exceed 4 hours; the reactor is heated to 75-80℃, and then 7kg of bis-2-methoxyethyl azodicarboxylate is added to the reactor, and stirring is started at a speed of 200r / min. After 0.5h, cooling is started. When the temperature drops to 39-42℃, the temperature is maintained, and the speed is adjusted to 80r / min and stirring is continued for 1h; stirring is continued at a temperature of 39-42℃ and a speed of 80r / min, and 15kg 3,3'-methylenebis(5-methyloxazoline) was stirred for 0.5h and then allowed to stand and cool to obtain a light yellow uniform transparent liquid, which was the highly efficient total sulfur remover for oil fields.

[0076] The desulfurization test results of the finished total desulfurizer for oil field prepared in Example 5 in the water phase and oil phase system (each group of experiments was repeated 2 times) are shown in the following Table 5:

[0077] Table 5

[0078]

[0079]

[0080] Compared with Example 3, this Example 5 does not add 3-methylpyridine and propylene glycol block polyether L61. The desulfurization test results of the desulfurization agent finished product finally prepared in Example 5 under the water phase and oil phase system are slightly worse than those of the desulfurization agent finished product prepared in Example 3, which is slightly more obvious for the desulfurization of gaseous sulfides such as hydrogen sulfide and methyl mercaptan. The reason is that this product system without adding defoamer components such as propylene glycol block polyether L61 will have a weaker foaming effect, which will have some negative effects on the desulfurization effect, and gaseous sulfides are relatively easier to generate bubbles than liquid and solid sulfides, and the foaming property of the product with the addition of defoamer components is suppressed, so the desulfurization effect of the product system of this application will be slightly better when defoamer components such as propylene glycol block polyether L61 are added.

[0081] After many tests, we found that the total sulfur removal agent of the present application has a slightly stronger ability to remove the same type of sulfides in an aqueous environment than in an oil phase environment, and has a slightly stronger ability to remove the same type of sulfides with short carbon chains than those with long carbon chains. This may be due to the solubility of the product and the steric hindrance caused by the carbon chain length. The total sulfur removal agent obtained by different component ratios in the present application will have slightly different emphases on the types of sulfide removal. The strongest formula for removing hydrogen sulfide and mercaptan will not be the same as the strongest formula for removing cyclic sulfide and chain sulfide. However, in general, for the common oil well desulfurization needs with hydrogen sulfide and mercaptan as the main components and other sulfides as the auxiliary components, the reaction product of paraformaldehyde and 2,2'-oxydiethanol with ammonia and morpholine derivative residues is polymerized in a mass ratio of (54.5-70):100, preferably in a mass ratio of (54.5-65):100, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethyl The combination of glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether as components is the best, wherein the mass ratio of paraformaldehyde, the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethyl azodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether is (18-21):(30-33):(14-16):(7-8):(22-24):(2-3):1, preferably (18-21):(30-33):15:7:23:3:1, and more preferably 20:31:15:7:23:3:1. Because it has excellent scavenging effects on hydrogen sulfide and mercaptans, it also has good effects on removing cyclic sulfides and chain sulfides, and has a good overall balance in scavenging effects on different types of sulfides and a high comprehensive value.

[0082] The above description of the embodiments is to facilitate the understanding and use of the present invention by those of ordinary skill in the art. It is obvious that those familiar with the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments. Improvements and modifications made by those skilled in the art based on the principles of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A total sulfur removal agent for oil fields, characterized in that: The invention comprises a product of a polymerization reaction of paraformaldehyde with a reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (53-70):100 and diethylene glycol monobutyl ether, wherein the mass ratio of the reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue and diethylene glycol monobutyl ether is (52-55):(16-18); The total sulfur removal agent is used as a desulfurization agent for hydrogen sulfide, chain sulfide and cyclic sulfide in a water-based and / or oil-based system.

2. The total sulfur removal agent for oil fields according to claim 1, characterized in that: The mass ratio of the reaction product of 2,2'-oxydiethanol with ammonia and a residue of a morpholine derivative to diethylene glycol monobutyl ether is 54:

17.

3. A total sulfur removal agent for oil fields, characterized in that: It includes a product of polymerization reaction of paraformaldehyde with a reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (54.5-70):100, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate and diethylene glycol monobutyl ether, wherein the mass ratio of paraformaldehyde, the reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate and diethylene glycol monobutyl ether is (18-21):(30-33):(14-16):(7-8):(22-24); The total sulfur removal agent is used as a desulfurizer for hydrogen sulfide, chain sulfides, cyclic sulfides and mercaptans in a water-based and / or oil-based system.

4. A total sulfur removal agent for oil fields, characterized in that: The invention comprises a product of polymerization reaction of paraformaldehyde with a reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (54.5-70):100, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether, wherein the mass ratio of paraformaldehyde, the reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether is (18-21):(30-33):(14-16):(7-8):(22-24):(2-3):1; The total sulfur removal agent is used as a desulfurizer for hydrogen sulfide, chain sulfides, cyclic sulfides and mercaptans in a water-based and / or oil-based system.

5. A total sulfur removal agent for oil fields, characterized in that: The invention is composed of the following components: a product of polymerization reaction of paraformaldehyde with a reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue in a mass ratio of (54.5-70):100, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether, wherein the mass ratios of the reaction product of paraformaldehyde, 2,2'-oxydiethanol with ammonia and a morpholine derivative residue, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine and propylene glycol block polyether are (18-21):(30-33):(14-16):(7-8):(22-24):(2-3):1; The total sulfur removal agent is used as a desulfurizer for hydrogen sulfide, chain sulfides, cyclic sulfides and mercaptans in a water-based and / or oil-based system.

6. The total sulfur removal agent for oil fields according to any one of claims 4 to 5, characterized in that: The mass ratio of the polymerization reaction of paraformaldehyde and the reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue is (54.5-65):100; and / or Among them, the mass ratios of paraformaldehyde, the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine, and propylene glycol block polyether are (18-21):(30-33):15:7:23:3:

1.

7. The total sulfur removal agent for oil fields according to claim 6, characterized in that: The mass ratio of paraformaldehyde, the reaction product of 2,2'-oxydiethanol with ammonia and a morpholine derivative residue, 3,3-methylenebis(5-methyloxazoline), bis-2-methoxyethylazodicarboxylate, diethylene glycol monobutyl ether, 3-methylpyridine, and propylene glycol block polyether is 20:31:15:7:23:3:

1.

8. The total sulfur removal agent for oil fields according to any one of claims 1 to 5, characterized in that: The polymerization reaction is carried out at a temperature of 60-65°C and a reaction time of 3-4 hours; and / or The polyformaldehyde is a polymer synthesized using formaldehyde as a monomer, and has a molecular weight of 360.

9. The total sulfur removal agent for oil fields according to any one of claims 4 to 5, characterized in that: The average molecular weight of the propylene glycol block polyether is 1800-2100, and the viscosity at 20° C. is 250-300 cPs.

10. The total sulfur removal agent for oil fields according to claim 9, characterized in that: The propylene glycol block polyether is propylene glycol block polyether L61.

11. A method for preparing a total sulfur removal agent for oil fields as claimed in any one of claims 1 to 10, characterized in that: The steps include: Step 1: Add the reaction product of 2,2'-oxydiethanol with ammonia and morpholine derivative residues into a reaction kettle containing diethylene glycol monobutyl ether, stir evenly, then slowly add paraformaldehyde, control the temperature at 60-65°C to carry out polymerization reaction for 3-4h, until all the solids in the system are dissolved; Step 2: Heat the reactor to 75-80°C, then add bis-2-methoxyethyl azodicarboxylate into the reactor, stir until it is dissolved, and cool to 39-42°C; Step 3: Add 3,3'-methylenebis(5-methyloxazoline) to the reaction kettle, stir until it is dissolved, then add 3-methylpyridine and propylene glycol block polyether, stir, and then let stand and cool to room temperature to obtain a light yellow uniform transparent liquid, which is the total sulfur remover for oil fields.

12. Use of the total sulfur remover for oil fields according to any one of claims 1 to 10 or the total sulfur remover for oil fields prepared by the method according to claim 11 in desulfurization of oil and gas fields.

13. Use of the total sulfur remover for oil fields according to any one of claims 1 to 10 or the total sulfur remover for oil fields prepared by the method according to claim 11 in desulfurization of oil and gas fields, wherein the total sulfur remover is used as a desulfurizer for hydrogen sulfide, chain sulfides, cyclic sulfides and mercaptans in water-based and / or oil-based systems; and / or The operating temperature is 2~96℃; and / or The added amount of the total sulfur removal agent is 5000±20ppm.

14. The use according to claim 13, characterized in that The operating temperature is 30℃~40℃.

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