CN104841492A - Vulcanizing agent preparing and deodorizing method for hydrogenation catalyst ex-situ pre-vulcanizing - Google Patents
Vulcanizing agent preparing and deodorizing method for hydrogenation catalyst ex-situ pre-vulcanizing Download PDFInfo
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Abstract
The present invention discloses a vulcanizing agent preparing and deodorizing method for hydrogenation catalyst ex-situ pre-vulcanizing. The vulcanizing agent preparing and deodorizing method comprises vulcanizing agent synthesis and vulcanizing agent deodorizing, wherein excessive ammonia water is adopted as a catalyst, isobutene and sulphur are subjected to addition to produce the main product vulcanizing agent and concurrently produce the byproduct isobutyramide, and the physical method treatment technology of gas stripping and the chemical method treatment technology of hydrogen peroxide oxidation and ethylene carbonate treatment are used to carry out combined deodorizing on the vulcanizing agent. According to the present invention, the physical method treatment technology of the gas stripping and the chemical method treatment technology of the hydrogen peroxide oxidation and the ethylene carbonate treatment are used to carry out combined deodorizing, such that mercaptan, thioketone, thio thioketone and other odor components in the coarse vulcanizing agent product can be effectively removed so as to effectively reduce the odor; and after the reaction, the catalyst and the product are easily separated, the ammonia water can be recovered and recycled, the wastewater and the waste gas are not produced, only a small amount of the waste residue is produced during the filtering, and the isobutyramide product with the purity of more than 95% can be obtained by carrying out the crystallization purification treatment on the waste residue.
Description
Technical field
The present invention relates to a kind of synthesis of Petroleum Refining Additives and rear refinement treatment, especially a kind of vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst and deodour method.
Background technology
Hydrobon catalyst ex situ presulfiding has that cure time is short, vulcanizing agent utilization rate is high, the active high of sulfuration rear catalyst, has become the Main way of pre-curing technology development.The vulcanizing agent mainly organic polysulfide of ex situ presulfiding, the one class sulfur-containing compound of its to be general formula be R-Sn-R1, n is generally 3 ~ 20, R and R1 can be identical or different, each representative is with the organic group of 1 ~ 150 carbon atom, such vulcanizing agent has that toxicity is low, the feature of decomposition temperature wide ranges, has and apply more widely in the outer pre-vulcanization process of hydrogenating catalyst.
Usual employing alkene and halogenation sulphur are that organic polysulfide prepared by raw material, halogenation sulphur and alkene generate the compound of sulfur-bearing, halogen atom under catalyst action, purer polysulfide product is obtained again, owing to releasing a large amount of HCl, H in reaction through dehalogenation atom operation
2the severe corrosive gases such as S, add waste water, waste residue (containing NaCl and sulfide), make three-protection design difficulty.
Organic polysulfide can also make mercaptan and sulphur carry out reacting preparing under base catalyst effect.Traditional catalyst has the organic base such as amine, alkanolamine, the method adopting mercaptan and sulphur oxidation reaction in the basic conditions to prepare polysulfide can obtain the organic polysulfide of different sulfur-crosslinked number, but the R and D cost of catalyst makes valuable product.
Summary of the invention
The object of the invention is the deficiency existed for the preparation method of vulcanizing agent in prior art, a kind of vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst and deodour method are provided, the inventive method comprises the synthesis of vulcanizing agent and the deodorization of vulcanizing agent, use excess of ammonia water as catalyst, the many sulfur products of saturated di-t-butyl (sulfur content is between 40% ~ 60%) are generated as major product vulcanizing agent after isobutene and sulphur addition, generate byproduct isobutyramide simultaneously, use the Physical treatment technology of air lift, hydrogen peroxide oxidation, the chemical Treatment technology of ethylene carbonate process carries out combination deodorization to vulcanizing agent.
The present invention is achieved by the following technical solutions:
For vulcanizing agent preparation and the deodour method of the outer presulfurization of hydrogenating catalyst, comprise following preparation process:
(1), the synthesis of vulcanizing agent: add in reactor by sulphur and ammoniacal liquor, be heated to 150 ~ 180 DEG C, reaction generates the polysulfide of ammonia; Then isobutene is passed in reactor, react 1 ~ 2 hour at 150 ~ 180 DEG C in pressure 3 ~ 9MPa, temperature; Be cooled to room temperature after reaction terminates, discharging is separated, and obtains organic phase and inorganic phase, and organic phase is filtered and obtained thick vulcanizing agent product; Wherein, described ammonia concn is 10% ~ 30%, and described sulphur, ammoniacal liquor are (with NH
3meter) and the ratio of amount of substance of isobutene be 0.5 ~ 2.0:0.2 ~ 2.0:1;
(2), the deodorization of vulcanizing agent: thick vulcanizing agent product carries out deodorization process in such a way and obtains vulcanizing agent product: nitrogen or air air lift, hydrogen peroxide process, ethylene carbonate process, air-distillation, or hydrogen peroxide process, ethylene carbonate process, nitrogen or air air lift, air-distillation, or ethylene carbonate process, hydrogen peroxide process, nitrogen or air air lift, air-distillation, or hydrogen peroxide process, ethylene carbonate process, air-distillation, nitrogen or air air lift, or ethylene carbonate process, hydrogen peroxide process, air-distillation, nitrogen or air air lift,
Described stripping temperature is 25 DEG C of (normal temperature) ~ 80 DEG C, and the air lift time is 10min ~ 60min; The temperature of described hydrogen peroxide process is 25 DEG C ~ 100 DEG C, processing time is 10min ~ 60min, hydrogen peroxide concentration is the hydrogen peroxide of 10% ~ 30%, the addition of hydrogen peroxide is 0.5% ~ 10% (accounting for the mass percent of thick vulcanizing agent product, lower same) of described thick vulcanizing agent product quality; The treatment temperature of described ethylene carbonate process is 25 DEG C ~ 80 DEG C, and the processing time is 10min ~ 60min, and the addition of ethylene carbonate is 0.5% ~ 10% of described thick vulcanizing agent product quality; Under nitrogen protection, carry out under 100 DEG C ~ 110 DEG C conditions, distillation time is 30min ~ 120min in described air-distillation.
In step (1), sulphur and ammoniacal liquor are heated to 150 ~ 180 DEG C after adding reactor, and constant temperature stirs 0.5 ~ 2 hour, sulphur is fully mixed with ammoniacal liquor, reacts the polysulfide generating ammonia.After temperature reaches 150 DEG C, first sulphur be cracked into the group of the free radicals such as two sulphur, trithio, four sulphur, five sulphur, six sulphur and ionic, then the polysulfide of unstable ammonia is generated with ammoniacal liquor reaction, after passing into isobutene, the polysulfide of ammonia and isobutene stirring reaction at pressure 3 ~ 9MPa, temperature 150 ~ 180 DEG C generates stable di-t-butyl polysulfide product for 1 ~ 2 hour.Select isobutene to be because other alkene character is good not as isobutene as raw material, and product is unstable, especially photostability and poor storage stability, easily analyse sulphur.
Preferably, described ammonia concn is 15% ~ 25%, and described sulphur, ammoniacal liquor are (with NH
3meter) and the ratio of amount of substance of isobutene be 1.2 ~ 1.7:0.5 ~ 1.0:1.
After reaction terminates, in reactor, generally upper strata is organic phase, and lower floor is inorganic phase, and adopt natural subsidence mode to be separated and obtain inorganic phase and organic phase, organic phase obtains thick vulcanizing agent product after crossing and filtering insoluble solid impurities; Air-distillation in distilling apparatus after inorganic phase filtering and impurity removing, control vapo(u)rizing temperature and be no more than 110 DEG C, preferable temperature is 60 ~ 110 DEG C, the ammonia produced when absorbing distillation with water (wherein for absorbing 20% ~ 40% of the quality of ammoniacal liquor used when the quality of the water of ammonia is synthesis vulcanizing agent) and water, reclaim the low concentration ammonia water circulation obtaining concentration 10% ~ 15% to use, this low concentration ammoniacal liquor can further across fresh ammonia enrichment to 15% ~ 25% of absorption; The still that distillation produces is residual is the thick isobutyramide of accessory substance, adopts water, ethanol or other medium to carry out 2 ~ 4 crystallization purifyings and obtains isobutyramide product.Consider from economy and crystallization effect angle, preferably, described thick isobutyramide water carries out crystallization purifying, and concrete operations are: thick isobutyramide product and water are mixed according to mass fraction 1 ~ 5:1 ~ 10, be heated to 60 DEG C ~ 90 DEG C, stir after dissolving completely, slowly be cooled to crystallizing at room temperature, filter and obtain primary crystallization product, purity is greater than 90%, adopt same method to carry out 2 ~ 3 crystallizations to primary crystallization product, obtain the isobutyramide product that purity is greater than 95%.
Inventor studies the ammonia finding to be reclaimed at most 80% by air-distillation, and 20% ammonia in addition, the water of 20% and isobutene reaction generate accessory substance isobutyramide product.
In step (2), the preferred version of the deodorization of vulcanizing agent is: thick vulcanizing agent product carries out nitrogen or air air lift successively, vulcanizing agent product is prepared in hydrogen peroxide oxidation, ethylene carbonate process, air-distillation, and concrete operations comprise: thick vulcanizing agent product DEG C is carried out air lift 30min ~ 60min with nitrogen or air 25 DEG C of (normal temperature) ~ 80; Then the hydrogen peroxide that concentration is 10% ~ 30% is added, the addition of hydrogen peroxide is that 0.5% ~ 10% of described thick vulcanizing agent product quality (accounts for the mass percent of thick vulcanizing agent product, lower same), at 25 DEG C ~ 85 DEG C stir process 30min ~ 60min; Add ethylene carbonate again, the addition of ethylene carbonate is 0.5% ~ 10% of described thick vulcanizing agent product quality, at 50 DEG C ~ 80 DEG C stir process 30min ~ 60min; Finally under 100 DEG C ~ 110 DEG C conditions, air-distillation 30min ~ 80min removes effumability light component and the water etc. such as unreacted isobutene, di-t-butyl list thioether under nitrogen protection, obtains vulcanizing agent product.
The concentration of described hydrogen peroxide is preferably 20% ~ 30%, and the addition of described hydrogen peroxide is preferably 1% ~ 5% of described thick vulcanizing agent product quality; The addition of described ethylene carbonate is preferably 1% ~ 5% of described thick vulcanizing agent product quality.
The concentration of described hydrogen peroxide most preferably is 30%.
Vulcanizing agent is single sulphur or polysulfide, belong to thioether and ether polysulfide, pure vulcanizing agent not unpleasant stink or taste very little, but due in the process of synthesis vulcanizing agent, sulphur and isobutene are at water, the unpleasant sulfur byproduct species of a part can be generated (as mercaptan under the existence of ammonia, thioketones and sulfo-thioketones etc.), this accessory substance is dissolved in vulcanizing agent, thick vulcanizing agent product odour is caused to be difficult to hear, particularly low-molecular-weight, volatile mercaptan, thioketones or sulfo-thioketones are (as 1, 2-bis-sulfo--3-thioketones, 4-methyl isophthalic acid, 2-bis-sulfo--3-thioketones etc.) etc., so deodorization process must be carried out by physico-chemical process to vulcanizing agent.Mercaptan in the vulcanizing agent synthesized under different reaction conditions, thioketones are different with sulfo-thioketones content, and usually, in described thick vulcanizing agent product, mercaptans content is 0.01% ~ 1%, and thioketones and sulfo-thioketones total content are 5% ~ 20%.Adopt nitrogen or air air lift, object is remove portion low-molecular-weight, volatile isobutyl mercaptan etc., stripping temperature controls at 25 DEG C ~ 80 DEG C, air lift time 10min ~ 60min, air lift can be carried out in the equipment such as special gas stripper or air lift still, a pipe can be inserted or put one at still base fabric in vulcanizing agent and evenly make leachy endless tube and make gas uniform distribute as far as possible, gas is from bottom to top through thick vulcanizing agent medium, light component is taken out of with bubbling form, gas flow rate controls be enough to make thick vulcanizing agent " boiling ", thus reaches deodorization object.Hydrogen peroxide oxidation process, in order to the sulfur-containing compound of easily oxidation precipitation under the sulfur-containing compound of easily separating out in instability, storage process in thick vulcanizing agent or illumination condition is carried out oxidation processes, accelerate the oxidation Decomposition of this kind of material, generate the sediments such as sulphur, such precipitation is removed after filtration from system, meanwhile, hydrogen peroxide also has certain decolorization, and product colour is shoaled.Process with ethylene carbonate, main purpose is in order to more active and unpleasant thioketones and sulfo-thioketones etc. in thick vulcanizing agent product are changed into the little and stable thio-ether type compounds of taste (belonging to product component) through adding thermal response, this is relatively simpler than other such as solvent refining or solvent extraction, and effect is also more satisfactory.Hydrogen peroxide and ethylene carbonate process are carried out in common autoclave stirred reactor.
The sulfur content of the vulcanizing agent product prepared through the inventive method is 40% ~ 60%; Described vulcanizing agent product is the many sulfur products of di-t-butyl, comprises the di-tert-butyl disulfide of 5 ~ 20%, 20 ~ 40% di-t-butyl trithioethers, 30 ~ 50% di-t-butyl four thioethers, 20 ~ 40% di-t-butyl five thioethers.
Beneficial effect of the present invention:
The inventive method is adopted to use excess of ammonia water as catalyst, the many sulfur products of saturated di-t-butyl are generated as vulcanizing agent after isobutene and sulphur addition, use the Physical treatment technology of air lift, the chemical Treatment technology of hydrogen peroxide oxidation, ethylene carbonate process carries out combination deodorization, effectively can remove the malodor components such as the mercaptan in thick vulcanizing agent product, thioketones and sulfo-thioketones, thus effectively reducing smell, the vulcanizing agent product sulfur content prepared is high, smell is low, corrosivity is little.
In the inventive method, catalyst activity is high, easily, ammoniacal liquor is recyclable to be recycled, and does not produce waste water and waste gas for post catalyst reaction and product separation, only produce the waste residue of seldom amount when filtering, and waste residue can obtain by crystallization purifying process the isobutyramide product that purity is greater than 95%.
Detailed description of the invention
In conjunction with detailed description of the invention, technical scheme of the present invention is described further.
Embodiment 1
The synthesis of vulcanizing agent: (concentration 25%, 153g, with NH by sulphur (86.4g, 2.7mol) and ammoniacal liquor
3meter 2.25mol) add in autoclave, be heated to 170 DEG C, constant temperature stirs 1 hour (during this, reactor pressure is about 2MPa), and reaction generates the polysulfide of ammonia; Then by isobutene (126g, 2.25mol) pump in reactor, after passing into isobutene, reactor pressure rises to more than 3MPa, controlled pressure is no more than 9MPa, 170 DEG C of stirring reactions 1 hour, then be cooled to room temperature, discharging natural subsidence mode is separated, obtain organic phase and inorganic phase, organic phase is filtered and obtains thick vulcanizing agent product (184g); Inorganic phase carries out air-distillation after filtering, and the ammonia produced when absorbing distillation with 40g water and water, reclaim and obtain the ammoniacal liquor that concentration is 15%; The still that distillation produces is residual is the thick isobutyramide of byproduct, thick isobutyramide and water carry out crystallization according to mass fraction 1:2, be heated to 80 DEG C ~ 90 DEG C stir completely dissolve after, be slowly cooled to crystallizing at room temperature, repeat crystallization four times according to the method described above, after purification, obtain the isobutyramide that purity is 99%.
The deodorization of vulcanizing agent: thick vulcanizing agent product (184g) is used nitrogen air lift 30min under normal temperature (25 DEG C); Thick vulcanizing agent product after air lift is placed in autoclave stirred reactor, adds the hydrogen peroxide 3.7g (for 2% of thick vulcanizing agent product quality) that concentration is 30%, at 85 DEG C of stir process 30min, crosses the precipitation filtering hydrogen peroxide oxidation process and produce; Add ethylene carbonate 3.7g (for 2% of thick vulcanizing agent product quality) again, at 80 DEG C of stir process 30min; Last air-distillation 60min at 100 DEG C ~ 110 DEG C temperature under nitrogen protection, obtains vulcanizing agent product (175g).
Embodiment 2
The synthesis of vulcanizing agent: (concentration 25%, 153g, with NH by sulphur (122.4g, 3.825mol) and ammoniacal liquor
3meter 2.25mol) add in autoclave, be heated to 170 DEG C, constant temperature stirs 1 hour, and reaction generates the polysulfide of ammonia; Then by isobutene (126g, 2.25mol) pump in reactor and react, controlled pressure is between 3 ~ 9MPa, 170 DEG C of stirring reactions 1 hour, be cooled to room temperature again, discharging natural subsidence mode is separated, and obtains organic phase and inorganic phase, organic phase is filtered and obtains thick vulcanizing agent product (210g); Inorganic phase process is with embodiment 1, and reclaim and obtain the low concentration ammoniacal liquor that concentration is 13%, purity is the isobutyramide of 99%.
The deodorization of vulcanizing agent: thick vulcanizing agent product (210g) is used nitrogen air lift 60min at normal temperatures; Thick vulcanizing agent product after air lift is placed in autoclave stirred reactor and adds the hydrogen peroxide 2.1g (for 1% of thick vulcanizing agent product quality) that concentration is 30%, at 60 DEG C of stir process 60min, crosses the precipitation filtering hydrogen peroxide oxidation process and produce; Add ethylene carbonate 2.1g (for 1% of thick vulcanizing agent product quality) again, at 50 DEG C of stir process 60min; Last air-distillation 60min at 100 DEG C ~ 110 DEG C temperature under nitrogen protection, obtains vulcanizing agent product (192g).
Embodiment 3
The synthesis of vulcanizing agent: (concentration 25%, 76.5g, with NH by sulphur (86.4g, 2.7mol) and ammoniacal liquor
3meter 1.125mol) add in autoclave, be heated to 170 DEG C, constant temperature stirs 1 hour, and reaction generates the polysulfide of ammonia; Then by isobutene (126g, 2.25mol) pump in reactor and react, controlled pressure is between 3 ~ 9MPa, 170 DEG C of stirring reactions 1 hour, be cooled to room temperature again, discharging natural subsidence mode is separated, and obtains organic phase and inorganic phase, organic phase is filtered and obtains thick vulcanizing agent product (188g); Inorganic phase carries out air-distillation after filtering, and the ammonia produced when absorbing distillation with 30g water and water, reclaim and obtain the ammoniacal liquor that concentration is 12%; The still that distillation produces is residual is the thick isobutyramide of byproduct, thick isobutyramide and water carry out crystallization according to mass fraction 1:2, be heated to 80 DEG C ~ 90 DEG C stir completely dissolve after, be slowly cooled to crystallizing at room temperature, repeat crystallization twice according to the method described above, purify and obtain the isobutyramide that purity is 96%.
The deodorization of vulcanizing agent: thick vulcanizing agent product (188g) is carried out air lift 30min with air at normal temperatures; Thick vulcanizing agent product after air lift is placed in autoclave stirred reactor, adds the hydrogen peroxide 9.4g (for 5% of thick vulcanizing agent product quality) that concentration is 30%, at 25 DEG C of stir process 30min, crosses the precipitation filtering hydrogen peroxide oxidation process and produce; Add ethylene carbonate 9.4g (for 5% of thick vulcanizing agent product quality) again, at 80 DEG C of stir process 30min; Last air-distillation 60min at 100 DEG C ~ 110 DEG C temperature under nitrogen protection, obtains vulcanizing agent product (169g).
The vulcanizing agent that embodiment 1-3 obtains is the many sulfur products of di-t-butyl, with constituent contents such as its two sulphur of chromatogram ration analysis, trithio, four sulphur and five sulphur; Analyze sulfur content, flash-point, viscosity, the colourity of vulcanizing agent, the physical and chemical parameter of vulcanizing agent product is in table 1.
The composition of the vulcanizing agent product that table 1 embodiment 1-3 obtains and character
As shown in Table 1: the vulcanizing agent product odour that embodiment 1-3 prepares is low, corrosivity is little, sulfur content is up to 40% ~ 60%; Vulcanizing agent product comprises di-tert-butyl disulfide, 40 ~ 50% di-t-butyl trithioethers, 20 ~ 35% di-t-butyl four thioethers, 10 ~ 20% di-t-butyl five thioethers of 5 ~ 20%.From storing, the angle of transport and use safety considers, the outer presulfurization agent product flash-point of hydrogenating catalyst preferably can not lower than 100 DEG C, and kinematic viscosity can not be too large, otherwise mobility is too poor, be not easy to use, this product flash-point is greater than 110 DEG C, modest viscosity, can meet instructions for use.Compared with traditional presulfurization agent DMDS (DMDS), the decomposition temperature of product of the present invention is relatively low (lower than 170 DEG C), in pre-vulcanization process, can at a lower temperature by hydrogenation catalyst adsorption-decomposition function, reduce cure time, reaction bed temperature ascensional range is reduced, easy to use.
Claims (8)
1., for vulcanizing agent preparation and the deodour method of the outer presulfurization of hydrogenating catalyst, it is characterized in that comprising following preparation process:
(1), the synthesis of vulcanizing agent: add in reactor by sulphur and ammoniacal liquor, be heated to 150 ~ 180 DEG C, reaction generates the polysulfide of ammonia; Then isobutene is passed in reactor, react 1 ~ 2 hour at 150 ~ 180 DEG C in pressure 3 ~ 9MPa, temperature; Be cooled to room temperature after reaction terminates, discharging is separated, and obtains organic phase and inorganic phase, and organic phase is filtered and obtained thick vulcanizing agent product; Wherein, described ammonia concn is 10% ~ 30%, and the ratio of the amount of substance of described sulphur, ammoniacal liquor and isobutene is 0.5 ~ 2.0:0.2 ~ 2.0:1, and the amount of substance of described ammoniacal liquor is with NH in ammoniacal liquor
3meter;
(2), the deodorization of vulcanizing agent: thick vulcanizing agent product carries out deodorization process in such a way and obtains vulcanizing agent product: nitrogen or air air lift, hydrogen peroxide process, ethylene carbonate process, air-distillation, or hydrogen peroxide process, ethylene carbonate process, nitrogen or air air lift, air-distillation, or ethylene carbonate process, hydrogen peroxide process, nitrogen or air air lift, air-distillation, or hydrogen peroxide process, ethylene carbonate process, air-distillation, nitrogen or air air lift, or ethylene carbonate process, hydrogen peroxide process, air-distillation, nitrogen or air air lift,
Described stripping temperature is 25 DEG C ~ 80 DEG C, and the air lift time is 10min ~ 60min; The temperature of described hydrogen peroxide process is 25 DEG C ~ 100 DEG C, and the processing time is 10min ~ 60min, and hydrogen peroxide is the hydrogen peroxide of concentration 10% ~ 30%, and the addition of hydrogen peroxide is 0.5% ~ 10% of described thick vulcanizing agent product quality; The treatment temperature of described ethylene carbonate process is 25 DEG C ~ 80 DEG C, and the processing time is 10min ~ 60min, and the addition of ethylene carbonate is 0.5% ~ 10% of described thick vulcanizing agent product quality; Described air-distillation is carried out under nitrogen protection, 60 DEG C ~ 110 DEG C conditions, and distillation time is 30min ~ 120min.
2. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 1 and deodour method, it is characterized in that in step (1), described sulphur and ammoniacal liquor are heated to 150 ~ 180 DEG C after adding reactor, constant temperature stirs 0.5 ~ 2 hour, sulphur is fully mixed with ammoniacal liquor, reacts the polysulfide generating ammonia.
3. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 1 and deodour method, it is characterized in that in step (1), described ammonia concn is 15% ~ 25%, the ratio of the amount of substance of described sulphur, ammoniacal liquor and isobutene is 1.2 ~ 1.7:0.5 ~ 1.0:1, and the amount of substance of described ammoniacal liquor is with NH in ammoniacal liquor
3meter.
4. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 1 and deodour method, it is characterized in that in step (1), air-distillation in distilling apparatus after described inorganic phase filtering and impurity removing, vapo(u)rizing temperature 60 ~ 110 DEG C, the ammonia produced when absorbing distillation with water and water, reclaim the low concentration ammoniacal liquor obtaining concentration 10% ~ 15%; 20% ~ 40% of the quality of ammoniacal liquor used when the quality of water time wherein for absorbing ammonia is synthesis vulcanizing agent;
The still that distillation produces is residual is crude amide series products, and described crude amide series products adopts water, ethanol or other medium to carry out 2 ~ 4 crystallization purifyings and obtains o series products, and described amide-type product is isobutyramide.
5. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 4 and deodour method, it is characterized in that described crude amide series products water carries out crystallization purifying, concrete operations are: crude amide series products and water are mixed according to mass fraction 1 ~ 5:1 ~ 10, be heated to 60 DEG C ~ 90 DEG C, stir after dissolving completely, slowly be cooled to crystallizing at room temperature, filtration obtains primary crystallization product, adopt same method to carry out 2 ~ 3 crystallizations to primary crystallization product, obtain isobutyramide product.
6. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 1 and deodour method, it is characterized in that in step (2), the deodorization of vulcanizing agent is: thick vulcanizing agent product carries out nitrogen or air air lift successively, vulcanizing agent product is prepared in hydrogen peroxide oxidation, ethylene carbonate process, air-distillation, and concrete operations comprise: thick vulcanizing agent product is carried out air lift 30min ~ 60min at 25 DEG C ~ 80 DEG C with nitrogen or air; Then add the hydrogen peroxide that concentration is 10% ~ 30%, the addition of hydrogen peroxide is 0.5% ~ 10% of described thick vulcanizing agent product quality, at 25 DEG C ~ 85 DEG C stir process 30min ~ 60min; Add ethylene carbonate again, the addition of ethylene carbonate is 0.5% ~ 10% of described thick vulcanizing agent product quality, at 50 DEG C ~ 80 DEG C stir process 30min ~ 60min; Last air-distillation 30min ~ 80min under 100 DEG C ~ 110 DEG C conditions under nitrogen protection, obtains vulcanizing agent product.
7. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 1 or 6 and deodour method, it is characterized in that the concentration of described hydrogen peroxide is 20% ~ 30%, the addition of described hydrogen peroxide is 1% ~ 5% of described thick vulcanizing agent product quality; The addition of described ethylene carbonate is 1% ~ 5% of described thick vulcanizing agent product quality.
8. the vulcanizing agent preparation for the outer presulfurization of hydrogenating catalyst according to claim 1 and deodour method, is characterized in that the sulfur content of described vulcanizing agent product is 40% ~ 60%; Described vulcanizing agent product is the many sulfur products of di-t-butyl, comprises the di-tert-butyl disulfide of 5 ~ 20%, 20 ~ 40% di-t-butyl trithioethers, 30 ~ 50% di-t-butyl four thioethers, 20 ~ 40% di-t-butyl five thioethers.
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| CN105315182A (en) * | 2015-11-09 | 2016-02-10 | 定远县云森科技有限公司 | Method for efficiently preparing ex-situ presulfuration agent through medium-pressure solvothermal method |
| CN114832869A (en) * | 2022-05-07 | 2022-08-02 | 银川兰达化工科技有限公司 | Organic vulcanizing agent and preparation method and application thereof |
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