CN114920674A - Method for preparing organic pre-vulcanizing agent at low cost - Google Patents
Method for preparing organic pre-vulcanizing agent at low cost Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 71
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011593 sulfur Substances 0.000 claims abstract description 69
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 2
- 229910020813 Sn-C Inorganic materials 0.000 claims 1
- 229910018732 Sn—C Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 33
- 239000002994 raw material Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000008116 organic polysulfides Chemical class 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention belongs to the field of synthesis and application of a pre-vulcanizing agent, and provides a method for preparing an organic pre-vulcanizing agent at low cost, which comprises the following steps: reacting refinery acid gas and refinery byproduct sulfur paste with isobutene in the presence of an alkaline catalyst to obtain a crude product; the content of hydrogen sulfide in the acid gas of the refinery is more than 92%, and the mass content of sulfur in the sulfur paste is more than 95%; washing the crude product with water, and separating to obtain an organic pre-vulcanizing agent; the sulfur content of the organic pre-vulcanizing agent is 55-65 wt%, the flash point is more than 110 ℃, and the decomposition temperature is more than 150 ℃. The invention adopts the cheap raw materials to prepare the high-value product organic pre-vulcanizing agent, solves the problems of the existing pre-vulcanizing agent, reduces the raw material cost of the pre-vulcanizing agent and improves the product quality. The preparation method has the advantages of simple preparation process, low raw material cost, high sulfur content of the product, high flash point, low decomposition temperature and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of a pre-vulcanizing agent, and particularly relates to a low-cost method for preparing an organic pre-vulcanizing agent.
Background
The prevulcanization mode of the hydrogenation catalyst is generally divided into in-situ prevulcanization and out-situ prevulcanization, and the prevulcanization agent is required to be used no matter which vulcanization mode is selected to treat the catalyst. Moreover, the selection of a proper pre-vulcanizing agent is very critical to the pre-vulcanizing process of the hydrogenation catalyst. In the traditional prevulcanization process, carbon disulfide (CS) is mostly used 2 ) Hydrogen sulfide (H) 2 S) and the like as a pre-vulcanizing agent. Conventional presulfiding agents have high sulfur contents, but these presulfiding agents have the following major disadvantages: firstly, the toxicity is high; secondly, the heat is released in a centralized way in the vulcanization process, so that the temperature runaway of a bed layer is easily caused, and the performance of the catalyst is influenced; and the flash point is low, so that the transportation and the storage are inconvenient, and the like.
For this reason, there are studies on the application of organic polysulfides in the field of pre-vulcanising agents, which generally have the following advantages: the sulfur content is higher than 55%; the flash point is high and is more than 100 ℃; the decomposition temperature range is wide and is between 150 ℃ and 300 ℃, and the concentrated heat release can be avoided; low toxicity and little smell. At present, in the preparation process of a plurality of organic polysulfides, Chinese patent document with application publication number CN 111925307A discloses a method for preparing an external presulfurizing agent by a mixed alkali method, which is to add monomer sulfur and a catalyst solution into a reaction kettle, perform nitrogen replacement, heat the mixture to 130-180 ℃, slowly add isobutene into the reaction kettle, perform constant-temperature reaction for 2-6 hours, after the reaction is finished, stand and separate the product, and filter an organic phase to obtain a presulfurizing agent finished product.
However, the quality of the product obtained by the synthesis method needs to be further improved, and the cost is high. Therefore, there is an urgent need for a low-cost method for synthesizing an organic polysulfide pre-vulcanizing agent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low-cost method for preparing an organic pre-vulcanizing agent, and the preparation method can improve the quality of a pre-vulcanizing agent product and reduce the production cost.
The invention provides a method for preparing an organic pre-vulcanizing agent with low cost, which comprises the following steps:
reacting acid gas of a refinery and byproduct sulfur paste of the refinery with isobutene in the presence of a basic catalyst at the temperature of 130-; the volume fraction of hydrogen sulfide in the acid gas of the refinery is more than 92%, and the mass content of sulfur in the sulfur paste is more than 95%;
washing the crude product with water, and separating to obtain an organic pre-vulcanizing agent; the sulfur content of the organic pre-vulcanizing agent is 55-65 wt%, the flash point is more than 110 ℃, and the decomposition temperature is more than 150 ℃.
In an embodiment of the invention, the refinery acid gas is an off-gas from a sewage stripping plant having a hydrogen sulfide content of 92-95%, a carbon dioxide content of 3-5%, and a hydrocarbon content of 1-2% by volume fraction.
In the embodiment of the invention, the sulfur mass content of the sulfur paste is more than or equal to 95 percent, the water content is less than 2 percent, the organic matter content is less than 1 percent, and the ash content is less than 1 percent.
In the examples of the present invention, the alkaline catalyst is refinery lye, wherein the hydroxide content is 1-2 wt% and the sulfide content is 8.12 wt%.
In the embodiment of the invention, the molar ratio of the sulfur paste to the isobutene is preferably 1.5-3.0: 1, and the molar ratio of the isobutene to the hydrogen sulfide of the acid gas of the refinery is 1.8-3.0: 1.
In the embodiment of the invention, the addition amount of the alkaline catalyst is 0.5-1.5 times of the mass of the sulfur.
In the embodiment of the invention, the method adopts a closed-loop circulation reaction device, the reaction temperature is controlled to be 140-160 ℃, the reaction pressure is 3.0-6.0MPa, and the reaction time is 2-5 h.
In the embodiment of the invention, the alkaline catalyst is separated after the reaction is finished, the obtained crude product is washed with water at room temperature, and the volume ratio of the crude product to the water is 3-1: 1.
In the embodiment of the invention, the organic pre-vulcanizing agent comprises C as the main component 4 -S n -C 4 N is more than or equal to 1 and less than or equal to 6; wherein C is 4 -S 1 -C 4 The content of (A) is less than 5%; c 4 -S 2 -C 4 The content of (A) is 10-15%; c 4 -S 3 -C 4 The content of (A) is 20-30%; c 4 -S 4 -C 4 The content of (A) is 30-40%; c 4 -S 5 -C 4 The content of (A) is 20-30%; c 4 -S 6 -C 4 The content of (A) is less than 5%.
In the embodiment of the invention, the color of the organic pre-vulcanizing agent is amber, the decomposition temperature is 151-159 ℃, and the density is 1.05-1.12g/cm 3 。
At present, the treatment process of acid gas in a refinery is mainly used for preparing sulfur and sulfuric acid or preparing sodium hydrosulfide, the treatment process is complex, the added value of products is low, and the valuable application of the acid gas is not facilitated. The low-quality sulfur paste is commonly used as a raw material for preparing sulfuric acid, and the added value of the same product is lower.
By comprehensively considering the factors, the invention fully utilizes the refinery acid gas (the content of hydrogen sulfide is more than 92 percent) and the byproduct sulfur paste (the content of sulfur is more than or equal to 95 weight percent) from the aspects of raw material cost and solving the disadvantages of the existing prevulcanizing agent, adopts isobutene as the raw material, and prepares the environment-friendly organic prevulcanizing agent under certain process conditions, and the quality of the organic prevulcanizing agent comprises the following steps: the sulfur content is 55-65 wt%, the flash point is more than 110 ℃, and the decomposition temperature is more than 150 ℃. The invention adopts the cheap raw materials to prepare the high-value product organic pre-vulcanizing agent, realizes the high-value utilization of the acid gas and the sulfur paste of the low-value refinery, solves the problems of the prior pre-vulcanizing agent on one hand, reduces the raw material cost of the pre-vulcanizing agent on the other hand, and improves the product quality through the optimization of process parameters. The preparation method has the advantages of simple preparation process and low raw material cost, and the product has the advantages of high sulfur content, high flash point, low decomposition temperature and the like, and can solve the problem of concentrated heat release of the pre-vulcanizing agent in the pre-vulcanizing process of the hydrogenation catalyst.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the invention discloses a low-cost method for preparing an environment-friendly organic pre-vulcanizing agent, which comprises the steps of reacting refinery acid gas and refinery byproduct sulfur paste with isobutene in the presence of an alkaline catalyst at the temperature of 130-; the volume fraction of hydrogen sulfide in the acid gas of the refinery is more than 92 percent, and the mass content of sulfur in the sulfur paste is more than or equal to 95 percent; washing the crude product with water, and separating to obtain an organic pre-vulcanizing agent; the sulfur content of the organic pre-vulcanizing agent is 55-65 wt%, the flash point is more than 110 ℃, and the decomposition temperature is more than 150 ℃.
The preparation method can improve the quality of the presulfurization agent product, has simple preparation process, can reduce the production cost, and is beneficial to popularization and application.
The invention adopts refinery acid gas and byproduct sulfur paste and isobutene (molecular formula C) 4 H 8 ) The organic pre-vulcanizing agent is used as a raw material to prepare the organic pre-vulcanizing agent, so that the valuable utilization of acid gas of a refinery and a byproduct of sulfur paste of a device can be realized. Petroleum refineries, also called simply refineries, are plants which use petroleum as raw material and use physical separation and/or chemical reaction methods to obtain various petroleum fuels, petroleum asphalt and other petroleum products and petrochemical raw materials in the petroleum refining industry. The crude oil contains a small amount of sulfur, nitrogen, oxygen and other elements, and is converted into harmful compounds in the refining process, and the harmful compounds are discharged along with gas or dissolved into water. In addition, since the petroleum refining process requires the use of chemicals (such as acids, bases), catalysts, and the like, various waste residues are generated.
The raw materials used in the embodiment of the invention are acid gas of a refinery, byproduct sulfur paste and isobutene; wherein the acid gas can be acid waste gas generated by a sewage stripping device, and concretely comprises 92-95% of hydrogen sulfide by volume, 3-5% of carbon dioxide by volume and 1-2% of hydrocarbon by volume. The sulfur paste is a byproduct of a desulfurization section of the hydrogen production device, and the purity is more than or equal to 95 wt%; the water content is less than 2%, the organic matter content is less than 1%, the ash content is less than 1%, and the total content of iron and arsenic is less than 1%. The isobutene can be a product of a C4 separation device, and the content of the isobutene is more than or equal to 95%.
In the embodiment of the invention, the preparation method of the organic pre-vulcanizing agent adopts a closed-loop circulating reaction device which can be a conventional device in the field; wherein the isobutene feed may be 10 ml/min. The catalyst adopted in the specific embodiment of the invention is alkali liquor of a refinery, wherein the content of sodium hydroxide is 1-2 wt%, the content of sodium sulfide is 8-12 wt%, and the addition amount of the catalyst is 0.5-1.5 times, preferably 0.8-1.2 times of the mass of sulfur; the used catalyst can be separated out and continuously returned to the alkali liquor treatment device of the refinery for recycling.
The production process parameters of the environment-friendly organic pre-vulcanizing agent provided by the embodiment of the invention comprise: the reaction temperature is 130-220 ℃, and the preferable reaction temperature is 140-160 ℃; the reaction pressure is 3.0-6.0MPa, and the preferable reaction pressure is 4.5-5.5 MPa; the reaction time is 2-5h, preferably 3 h. In the reaction system of the invention, the molar ratio of the sulfur to the isobutene can be 1.5-3.0: 1, and the preferable ratio of the sulfur to the isobutene is 2.0-2.5; the molar ratio of isobutene to hydrogen sulphide may be from 1.8 to 3.0: 1, preferably from 2.0 to 2.5: 1.
In the embodiment of the invention, a crude product is obtained by reacting in the presence of an alkaline catalyst, and a presulfurizing agent product is obtained by post-treatment. The post-treatment process of the crude product specifically comprises the following steps: separating out the alkaline catalyst after the reaction is finished, feeding the obtained crude product into a water washing kettle according to V Coarse ∶V Water (W) Distilled water is injected in the proportion of 3-1: 1, and after washing for 15min at room temperature, the product is obtained by separation; the washing wastewater can be reused or recycled after being treated by a sewage treatment device as a raw material.
In an embodiment of the present invention, theThe organic pre-vulcanizing agent comprises organic polysulfide C as main component 4 -S n -C 4 N is more than or equal to 1 and less than or equal to 6.
Wherein, C 4 -S 1 -C 4 The content of (A) is less than 5%; c 4 -S 2 -C 4 The content of (A) is 10-15%; c 4 -S 3 -C 4 The content of (A) is 20-30%; c 4 -S 4 -C 4 The content of (A) is 30-40%; c 4 -S 5 -C 4 The content of (A) is 20-30%; c 4 -S 6 -C 4 The content of (A) is less than 5%.
The quality of the environment-friendly organic pre-vulcanizing agent obtained by the embodiment of the invention comprises the following steps: the sulfur content is 55-65 wt%, the flash point is more than 110 ℃, the decomposition temperature is more than 150 ℃ (such as between 151 and 159 ℃), and the density can be 1.05-1.12g/cm 3 (ii) a The product is amber and has low odor. The synthesis method disclosed by the invention is simple in process and low in raw material cost, and the product has the advantages of high sulfur content, high flash point, small smell, low decomposition temperature (compared with the existing organic pre-vulcanizing agent, such as the DMDS decomposition temperature of 200 ℃, the standard pre-vulcanizing agent decomposition temperature of 160 ℃ and the like), and the like, so that the product quality is improved, and the problems of concentrated heat release and the like of the pre-vulcanizing agent in the pre-vulcanizing process of the hydrogenation catalyst are solved.
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention. In the following examples, the sulfur content of the sulfur paste is not less than 95%, the water content is less than 2%, the organic matter is less than 1%, the ash content is less than 1%, and the total content of iron and arsenic is less than 1% by mass. The acid gas is acid waste gas generated by a sewage stripping device, and comprises 92-95% of hydrogen sulfide, 3-5% of carbon dioxide and 1-2% of hydrocarbons according to volume fraction. Isobutene is a product of a C4 separation device, and the content is more than or equal to 95%. The catalyst is alkali liquor of refinery, wherein the content of sodium hydroxide is 1-2 wt%, and the content of sodium sulfide is 8-12 wt%.
Example 1
The sulfur content of the sulfur paste is 95 percent, the content of isobutene is 96.5 percent, the content of acid gas hydrogen sulfide is 92.4 percent, the feeding amount of isobutene is 10ml/min, the molar ratio of sulfur to isobutene is controlled to be 2.27: 1, and the molar ratio of hydrogen sulfide to isobutene is 1: 2.0; the adding amount of the catalyst is 1.0 time of the mass of the sulfur; controlling the reaction temperature at 150 ℃, the reaction pressure at 5.0MPa and the reaction time at 3h to obtain a crude product, and carrying out post-treatment to obtain an environment-friendly organic pre-vulcanizing agent product.
Wherein the post-treatment process comprises the following steps: separating out the catalyst solution after the reaction is finished, feeding the obtained crude product into a water washing kettle according to V Coarse ∶V Water (I) Adding distilled water at the ratio of 3: 1, washing with water at room temperature for 15min, and separating.
The product is amber and has low smell; the sulfur content was 57%, and the density was 1.05g/cm 3 The flash point was 112 ℃ and the total yield was 95.3%. The total yield is calculated by the formula:
total yield is m Mixed product /(m Catalyst and process for preparing same +m Isobutene +m Sulfur )*100％。
The main component of the environment-friendly organic pre-vulcanizing agent is C 4 -S n -C 4 (n is more than or equal to 1 and less than or equal to 6); wherein C 4 -S 1 -C 4 The content of (A) is less than 5%; c 4 -S 2 -C 4 The content of (A) is 10% -15%; c 4 -S 3 -C 4 The content of (A) is 20% -30%; c 4 -S 4 -C 4 The content of (A) is 30-40%; c 4 -S 5 -C 4 The content of (A) is 20% -30%; c 4 -S 6 -C 4 The content of (A) is less than 5%. Content characterization: the content of each component was quantified by gas chromatography.
Example 2
99.4 percent of sulfur content of sulfur paste, 98.7 percent of isobutene content, 94.7 percent of acid gas hydrogen sulfide content, 10ml/min of isobutene feeding amount, 2.42: 1 of the mol ratio of the sulfur to the isobutene and 1: 2.5 of the mol ratio of the hydrogen sulfide to the isobutene; the adding amount of the catalyst is 1.0 time of the mass of the sulfur; the reaction temperature was controlled at 150 ℃, the reaction pressure 5.0MPa, and the reaction time 3h to obtain a crude product, which was worked up as in example 1.
The product is amber and has low smell; the contents of the components are similar to those in example 1, the sulfur content is 59%, and the density is 1.05g/cm 3 The flash point was 115 ℃ and the overall yield was 96.4%.
Example 3
99.4 percent of sulfur content of sulfur paste, 98.7 percent of isobutene content, 94.7 percent of acid gas hydrogen sulfide content, 10ml/min of isobutene feeding amount, 2.42: 1 of sulfolene molar ratio and 1: 2.5 of hydrogen sulfide and isobutene molar ratio; the adding amount of the catalyst is 1.0 time of the mass of the sulfur; the reaction temperature is controlled at 150 ℃, the reaction pressure is controlled at 5.5MPa, the reaction time is 3h, a crude product is obtained, and the product is obtained after the post-treatment (same as the example 1).
The product is amber and has low smell; the contents of the components are similar to those in example 1, the sulfur content is 60.7%, and the density is 1.08g/cm 3 The flash point was 115 ℃ and the total yield was 96.2%.
Example 4
99.4 percent of sulfur content of sulfur paste, 98.7 percent of isobutene content, 94.7 percent of acid gas hydrogen sulfide content, 10ml/min of isobutene feeding amount, 2.42: 1 of the mol ratio of the sulfur to the isobutene and 1: 2.5 of the mol ratio of the hydrogen sulfide to the isobutene; the adding amount of the catalyst is 1.0 time of the mass of the sulfur; the reaction temperature is controlled to 145 ℃, the reaction pressure is controlled to 5.5MPa, the reaction time is controlled to 3 hours, a crude product is obtained, and the product is obtained after the post-treatment (same as the example 1).
The product is amber and has low smell; the sulfur content is 60.6 percent, and the density is 1.07g/cm 3 The flash point was 116 ℃ and the total yield was 95.6%.
The above embodiment improves the product quality by optimizing the process parameters and preparing the high-value product organic pre-vulcanizing agent by using the raw materials with low price.
Example 5
The hydrogenation catalyst presulfurization condition is as follows: adopting the product of the scheme of the embodiment 1, preparing the organic pre-vulcanizing agent into refined diesel oil with the sulfur content of 1%, and pre-vulcanizing at low temperature: the temperature is 250 ℃ and 8 hours; high-temperature pre-vulcanization: the temperature is 320 ℃, and the time is 12 hours; volume space velocity: 2.0h -1 (ii) a Hydrogen-oil volume ratio: 600: 1; pressure: 6.0 MPa;
evaluation experimental conditions of the hydrogenation catalyst: raw material coking diesel oil; the reaction pressure is 6.0 MPa; volume space velocity of 2.0h -1 (ii) a The reaction temperature is 360 ℃; hydrogen to oil volume ratio 600.
The evaluation results were as follows:
TABLE 1 evaluation results of hydrogenation catalyst
Table 1 the data results show that: the environment-friendly organic pre-vulcanizing agent prepared by the invention has the same pre-vulcanizing effect as the pre-vulcanizing agent in the current industry, and can be used instead.
Therefore, the invention adopts the low-price raw materials to prepare the high-value product organic pre-vulcanizing agent, and realizes the high-value utilization of the acid gas and the sulfur paste in the low-value refinery. The preparation method has the advantages of simple preparation process and low raw material cost, and the product has the advantages of high sulfur content, high flash point, low decomposition temperature and the like, and can solve the problem of concentrated heat release of the pre-vulcanizing agent in the pre-vulcanizing process of the hydrogenation catalyst.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (10)
1. A method for preparing an organic pre-vulcanizing agent at low cost is characterized by comprising the following steps:
reacting acid gas of a refinery and byproduct sulfur paste of the refinery with isobutene in the presence of a basic catalyst at the temperature of 130-; the volume fraction of hydrogen sulfide in the acid gas of the refinery is more than 92 percent, and the mass content of sulfur in the sulfur paste is more than 95 percent;
washing the crude product with water, and separating to obtain an organic pre-vulcanizing agent; the sulfur content of the organic pre-vulcanizing agent is 55-65 wt%, the flash point is more than 110 ℃, and the decomposition temperature is more than 150 ℃.
2. The method of claim 1, wherein the refinery acid gas is an off-gas from a sewage stripping plant having a hydrogen sulfide content of 92-95%, a carbon dioxide content of 3-5%, and a hydrocarbon content of 1-2% by volume fraction.
3. The method of claim 1, wherein the sulfur paste has a sulfur mass content of 95% or more, a moisture content of < 2%, an organic matter content of < 1%, and an ash content of < 1%.
4. The process of claim 1, wherein the basic catalyst is a refinery lye having a hydroxide content of 1-2 wt% and a sulfide content of 8-12 wt%.
5. A process according to any one of claims 1-4, characterized in that the sulphur paste has a sulphur to isobutene molar ratio of 1.5-3.0: 1 and an isobutene to refinery acid gas hydrogen sulphide molar ratio of 1.8-3.0: 1.
6. The method of claim 5, wherein the basic catalyst is added in an amount of 0.5 to 1.5 times the mass of the sulfur.
7. The method according to any one of claims 1 to 4, wherein a closed cycle reaction device is adopted, the reaction temperature is controlled to be 140 ℃ to 160 ℃, the reaction pressure is controlled to be 3.0MPa to 6.0MPa, and the reaction time is 2h to 5 h.
8. A process according to any one of claims 1 to 4, wherein the basic catalyst is separated after the reaction is finished, and the crude product obtained is washed with water at room temperature, the volume ratio of the crude product to the water being 3-1: 1.
9. Process according to any one of claims 1 to 4, characterized in that the organic pre-vulcanizing agent consists essentially of C 4 -Sn-C 4 N is more than or equal to 1 and less than or equal to 6; wherein C 4 -S 1 -C 4 The content of (A) is less than 5%; c 4 -S 2 -C 4 The content of (A) is 10-15%; c 4 -S 3 -C 4 The content of (A) is 20-30%; c 4 -S 4 -C 4 The content of (A) is 30-40%; c 4 -S 5 -C 4 The content of (A) is 20-30%; c 4 -S 6 -C 4 The content of (A) is less than 5%.
10. The method as claimed in claim 9, wherein the organic pre-vulcanizing agent is amber in color, has a decomposition temperature of 151- 3 。
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