CN103801334B - A kind of preparation method of sulfurized hydrogenation catalyst - Google Patents
A kind of preparation method of sulfurized hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of sulfurized hydrogenation catalyst.The method comprises: adopt carrier predecessor and elementary sulfur, adjuvant kneading, shaping, and dry, load hydrogenation active metals component, then heat-treats, obtain sulfurized hydrogenation catalyst.The method preparation process is simple, cost is low.The cure efficiency of the sulfurized hydrogenation catalyst of gained is good, and hydrogenation activity is high.
Description
Technical field
The present invention relates to a kind of preparation method of sulfurized hydrogenation catalyst.
Background technology
Conventional hydrogenation catalyst is oxidation state, and really plays the material of active function for sulphided state, so need carry out sulfuration in reactor before use during actual use.This not only adds production cost, and sulfidation easily pollutes to human and environment, therefore the scientific research personnel of countries in the world actively seeks redress.Current research is mainly concentrated both ways: being ex situ presulfiding on the one hand, is directly prepare sulfide type catalyst on the other hand.Ex situ presulfiding refer to adopt distillation, vulcanizing agent introduces in the hole of oxidized catalyst by the method for melting or dipping, then under the existence of inert gas, catalyst member presulfurization is made through hyperthermic treatment, finally catalyst is loaded in reactor, complete the final presulfurization of catalyst in presence of hydrogen.The research of ex situ presulfiding is comparatively deep, and relevant report is also more, as the outer method for pre-sulphuration of EPRES hydrogenating catalyst etc. of Fushun Petrochemical Research Institute.Ex situ presulfiding technology is compared with sulfuration in device, there is catalyst activity high, save on-stream time, simplify Star-up, the advantages such as little are polluted to human and environment, but ex situ presulfiding is the same with in-situ presulfurization, in pre-vulcanization process under hydrogen effect, may there is hydrogenolysis in oxidized catalyst, and active component and carrier adhesion often too strong, hydrogenation catalyst can not be fully vulcanized, cause the activity of catalyst not improve further.Catalyst is through oxidation state presulfurization use again, and the production stage of catalyst is increased, and production cost strengthens, and directly affects the economy of technique.Therefore various countries very pay attention to the research directly preparing sulfide type catalyst.
US4,528,089 preparation method describing a kind of hydrodesulfurization and hydrodenitrogenation catalyst is raw material with ammonium thiomolybdate or hydrocarbylthio ammonium molybdate, and in airtight autoclave, hydrogen is obtained by reacting powder catalyst under existing.US4,650,563 first by the inorganic salts of nickel or cobalt and ammonium thiomolybdate and ethylenediamine mixing, and reaction under certain condition generates compound, then in containing the hydrogen of hydrogen sulfide, is obtained by reacting required catalyst.US7,132,386 report a kind of method preparing cobalt molybdenum sulfide type catalyst, first the mixing of ammonium thiomolybdate, cobalt chloride and alkyl bromination ammonia are generated intermediate product, then are moved in reactor, and at 300 DEG C, under 500psi hydrogen pressure, reaction generates MoS
2and Co
9s
8.US6, ammonium thiomolybdate is dissolved in organic solvent by 451,729, produces the non-loading type MoS of high-ratio surface under high-temperature hydrogen exists
2catalyst, the hydrogenation cracking activity of this catalyst is high.CN1569331A discloses a kind of modified cobalt molybdenum base sulfide catalyst and preparation method thereof, by preparation ammonium thiomolybdate solution, and co-precipitation molybdenum, cobalt and the third transition metal constituent element, under nitrogen protection roasting, obtained black powder catalyst.Prepared by above-mentioned technology is sulphided state catalyst, and unsupported catalyst is not suitable for using in large-scale hydrogenation reactor.
CN1557917A discloses a kind of sulfurized hydrogenation catalyst and preparation method thereof; the presoma of group vib metal M o and W is mainly incorporated in the hole of catalyst carrier for hydrgenating to the carrier of conventional catalyst by adopting solubility Thiomolybdate and thiqtung state solution by the preparation method of this catalyst; 350 DEG C of roastings 4 hours under nitrogen protection; again with containing Ni; the solution impregnation of Co; 350 DEG C of roastings 4 hours under nitrogen protection, thus the supported sulfide catalyst of preparation Mo, W, Co, Ni.This patent adopts two-step method Kaolinite Preparation of Catalyst, first form molybdenum bisuphide phase, after carried metal nickel, post-cure not easily forms highly active Co-Mo-S or Ni-Mo-S phase, and part metals nickel generates the nickel sulfide phase without hydrogenation activity, causes the waste of metallic nickel.Two one-step baking preparation technologies are loaded down with trivial details, less economical, are unfavorable for large-scale industrial production.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the sulfurized hydrogenation catalyst that a kind of preparation process is simple, cost is low.The cure efficiency of the sulfurized hydrogenation catalyst of gained is good, and hydrogenation activity is high.
The preparation method of sulfurized hydrogenation catalyst of the present invention, comprise: adopt carrier predecessor and elementary sulfur, adjuvant kneading, shaping, dry, load hydrogenation active metals component, then heat treatment in the presence of an inert gas, obtain sulfurized hydrogenation catalyst, the addition of wherein said elementary sulfur is 100wt% ~ 250wt% that catalyst theory needs sulfur content, be preferably 100wt% ~ 150wt%, adjuvant is unsaturated hydro carbons or the mixture containing unsaturated hydro carbons, the boiling point of adjuvant is 150 ~ 370 DEG C, the addition of adjuvant counts 3% ~ 50% of carrier predecessor butt weight with unsaturated hydro carbons, described heat treated condition is as follows: at inert gas, under at least one gas in hydrogen exists, treatment temperature is 200 ~ 600 DEG C, processing time is 2 ~ 15 hours.
In the preparation method of sulfurized hydrogenation catalyst of the present invention, carrier comprises the carrier component being conventionally used as hydrogenation catalyst, comprises aluminium oxide, silica, titanium dioxide, zirconia etc. one or more.Carrier predecessor refers to the compound before carrier component dehydration, is generally the hydroxide that carrier component is corresponding.In the inventive method, other ratio of component can also be added as one or more in molecular sieve, bentonite, kaolin, sepiolite etc.In order to obtain the special nature of required carrier, can add auxiliary agent as containing one or more in P, B, Si, F, Mg, Zn etc., auxiliary agent adds in conventional manner, such as the form of its oxide or salt, can add when preparing carrier predecessor, also can add when kneading.
Described adjuvant is unsaturated hydro carbons, comprise in alkene, alkadienes, alkynes one or more, also the mixture being rich in unsaturated hydro carbons can be selected, in such as coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil etc. one or more, wherein the concentration of unsaturated hydro carbons is 30v% ~ 60v%.
In the inventive method, when shaping, optionally can add shaping assistant, one or more in such as adhesive, extrusion aid.Described binding agent refers to various acids, comprise the inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid and the organic acid such as acetic acid, citric acid one or more.Extrusion aid refer in the materials such as sesbania powder, starch, talcum powder one or more.
In the inventive method, need to carry out drying after shaping, drying can be carried out in atmosphere, also can carry out under an inert gas, for ensureing the simplicity of process, preferably dry in atmosphere.Drying condition is as follows: 50 ~ 200 DEG C and baking temperature lower than the boiling point of adjuvant, dry 1 ~ 10 hour, be preferably 120 ~ 180 DEG C and baking temperature lower than the boiling point of adjuvant, dry 2 ~ 5 hours.
In sulfurized hydrogenation catalyst of the present invention, consumption and the ratio of hydrogenation active metals are well known to those skilled in the art, those skilled in the art can according to produced catalyst need specifically determine.Usually. with the weight of catalyst for benchmark, the content of hydrogenation active metals is 5wt% ~ 50wt%.In the inventive method, described hydrogenation active metals be group VIB, group VIII metal one or more.Group VIB metal is preferably Mo and/or W, and group VIII metal is preferably Ni and/or Co, and the content of preferred group VIB metal is 15% ~ 30%, and the content of group VIII metal is 1% ~ 6%.
In the inventive method, the method of described load hydrogenation active metals component can adopt conventional method, be generally kneading method or infusion process, wherein infusion process first prepares the maceration extract containing hydrogenation active metals, then above-mentioned maceration extract is flooded with the dry support after shaping, need drying after dipping, general drying condition is as follows: 50 ~ 200 DEG C and baking temperature lower than the boiling point of adjuvant, dry 1 ~ 10 hour.Kneading method is added in the mixture of carrier predecessor, elementary sulfur and adjuvant with the form of solid or the aqueous solution by the compound containing hydrogenation active metals component to carry out kneading, then through shaping and dry.Infusion process and kneading method can adopt this area conventional method to carry out.Described infusion process can pass through repeatedly the content of dipping, saturated dipping, excessive impregnating dipping technique adjustment activity over catalysts metal.
In the preparation method of sulfide type catalyst of the present invention, described heat treatment carries out under at least one gas in inert gas, hydrogen exists, preferred employing Fractional Heat-treatment, specific as follows: 200 ~ 280 DEG C of constant temperature process 0 ~ 5 hour, then at 290 ~ 350 DEG C, constant temperature process 1 ~ 5 hour, finally 360 ~ 600 DEG C of constant temperature process 1 ~ 5 hour.
Compared with prior art, tool has the following advantages the preparation method of sulfurized hydrogenation catalyst for refining of the present invention:
(1) catalyst is without oxidation state, and production technology is simple, and catalyst preparing cost is low;
(2) addition element sulphur and adjuvant in kneading process, then drying is carried out under certain conditions, be conducive to elementary sulfur to be like this combined with adjuvant, be easier to form high activity phase with hydrogenation active metals, and make sulphur evenly, be more stably present in carrier component.In heat treatment process; especially Fractional Heat-treatment is adopted; be conducive to adjuvant and water generates the oxy radicals such as aldehyde, carboxylic acid, alcohol or ketone; promote that hydrogenation active metals and sulphur form the active phase of highly active II class; and sulfuration obtain more completely, more abundant; and be converted in the process of sulphided state metal in hydrogenation active metals; simultaneously can generating portion gas; be conducive to improving the distribution of hydrogenation active metals and the pore structure of catalyst on catalyst; be conducive to the diffusion of raw material, and then effectively improve the hydrogenation activity of catalyst;
(3) catalyst is complete cure type catalyst, and directly heating up in presence of hydrogen goes into operation, and empty calory and hydrogen sulfide gas are released, and the outer pre-sulfide catalyst bed of effective preventer is easy to temperature runaway and the problem such as intensification initial stage device is airtight.
Accompanying drawing explanation
Fig. 1 is the TEM figure of sulfide type catalyst A;
Fig. 2 is the TEM figure of sulfide type catalyst B;
Fig. 3 is the TEM figure of sulfide type catalyst C;
Fig. 4 is the TEM figure of sulfide type catalyst D;
Fig. 5 is the TEM figure of sulfuration rear catalyst E;
Fig. 6 is the TEM figure of sulfuration rear catalyst F.
Detailed description of the invention
Concrete preparation method is as follows for sulfide type catalyst of the present invention:
Mode 1:
1, the preparation of catalyst carrier: adopt conventional method Kaolinite Preparation of Catalyst carrier predecessor, mixed with elementary sulfur, adjuvant, shaping assistant by carrier predecessor, extrusion on banded extruder, drying makes catalyst carrier.Drying can be carried out in atmosphere, also can carry out under an inert gas.Drying condition is: 50 ~ 200 DEG C of drying 2 ~ 10h;
2, the preparation of sulfide type catalyst
Active metal is made into the impregnation fluid carrier of desired concn and composition, then dry, drying condition is: 50 ~ 200 DEG C of drying 2 ~ 10h, also can natural air drying.Described heat treatment carries out under at least one gas in inert gas, hydrogen exists, treatment temperature is 200 ~ 600 DEG C, processing time is 2 ~ 15 hours, heat treatment preferably adopts segment processing, specific as follows: 200 ~ 280 DEG C of constant temperature process 0 ~ 5 hour, then at 290 ~ 350 DEG C, constant temperature process 1 ~ 5 hour, finally 360 ~ 600 DEG C of constant temperature process 1 ~ 5 hour.
Mode 2:
Active metal is introduced when preparing carrier, hydrogenation active metals salting liquid can be added when kneading, also hydrogenation active metals salt can be mixed with carrier predecessor, elementary sulfur, adjuvant, shaping assistant, shaping rear drying, drying condition is: 50 ~ 200 DEG C of drying 2 ~ 10h, then heat-treats.Described heat treatment carries out under at least one gas in inert gas, hydrogen exists, treatment temperature is 200 ~ 600 DEG C, processing time is 2 ~ 15 hours, heat treatment preferably adopts segment processing, specific as follows: 200 ~ 280 DEG C of constant temperature process 0 ~ 5 hour, then at 290 ~ 350 DEG C, constant temperature process 1 ~ 5 hour, finally 360 ~ 600 DEG C of constant temperature process 1 ~ 5 hour.
The technical characterstic that the invention is further illustrated by the following examples, but these embodiments can not limit the present invention.Wt% is mass fraction.
The preparation of embodiment 1 sulfide type catalyst A
(Shandong Alumina factory produces to take boehmite, butt is 73wt%) 900g, sesbania powder 19g, elementary sulfur powder 80g, citric acid 32g, hexene 54ml, nitric acid (weight concentration 30%) 48ml, silica gel (by weight containing silica 30%) 159ml, deionized water 250ml mixes, banded extruder is extruded into 1.2mm clover bar, in 150 DEG C of dryings 3 hours in air dry oven, obtains required catalyst carrier A.
Get containing ammonium molybdate and nickel nitrate solution (containing molybdenum oxide 30g/100ml; containing nickel oxide 5g/100ml) after impregnated carrier A in 150 DEG C of dryings 3 hours; heat-treat under nitrogen protection afterwards; first 240 DEG C are warming up to; constant temperature 2 hours; be warming up to 320 DEG C more afterwards, constant temperature 1 hour, be finally warming up to 450 DEG C of constant temperature 3 hours.The TEM of catalyst the results are shown in Figure 1.
The preparation of embodiment 2 sulfide type catalyst B
Identical with embodiment 1, just adjuvant is changed into the catalytic gasoline (presence of unsaturates is 49.8v%) of 100ml.The TEM of catalyst the results are shown in Figure 2.
The preparation of embodiment 3 sulfide type catalyst C
(Shandong Alumina factory produces to take boehmite; butt is 73wt%) 900g; sesbania powder 19g; sulphur powder 100g; citric acid 32g; laurylene 30ml, ammonium molybdate 245g, nickel nitrate 127g; nitric acid (weight concentration 30%) 48ml; silica gel (by weight containing silica 30%) 159ml, deionized water 250ml mixes, and banded extruder is extruded into 1.2mm clover bar; in 120 DEG C of dryings 5 hours in air dry oven; namely heat treatment under hydrogen shield afterwards, first 290 DEG C of constant temperature 2 hours, then obtain catalyst C in 3 hours at 400 DEG C of constant temperature.TEM the results are shown in Figure 3.
The preparation of embodiment 4 sulfide type catalyst D
Identical with embodiment 3, just employing one section of heat treatment, namely obtains catalyst D in 6 hours at 400 DEG C of constant temperature.TEM the results are shown in Figure 4.
The preparation of comparative example 1 oxidized catalyst E
(Shandong Alumina factory produces to take boehmite, butt is 73% by weight) 900g, sesbania powder 19g, citric acid 32g, nitric acid (weight concentration 30%) 48ml, silica gel (by weight containing silica 30%) 159ml, deionized water 250ml mixes, banded extruder is extruded into 1.2mm clover bar, and in 150 DEG C of dryings 3 hours in air dry oven, namely 600 DEG C of roastings obtain required catalyst carrier B in 3 hours.
Get containing after ammonium molybdate and nickel nitrate solution (containing molybdenum oxide 30g/100ml, containing nickel oxide 5g/100ml) impregnated carrier B in 150 DEG C of dryings 3 hours, in Muffle furnace, within 3 hours, namely obtain catalyst E in 500 DEG C of roastings afterwards.Catalyst TEM after sulfuration the results are shown in Figure 5.
The preparation of comparative example 2 ex situ presulfiding catalyst F
The elementary sulfur dissolved is introduced oxidized catalyst E, and the introduction volume of sulphur is 105% of theoretical amount, and then with diesel oil distillate dipping, its consumption is 40% of catalyst weight.180 DEG C process 3 hours at ambient pressure, obtain ex situ presulfiding catalyst F.Catalyst TEM after sulfuration the results are shown in Figure 6.
The activity of embodiment 4 sulfide type catalyst is investigated
Experiment completes on micro-reactor, and carrier gas is hydrogen.Feedstock oil is atmosphere 3rd side cut oil, and sulfur content 6524.1 μ g/g, nitrogen content is 50.6 μ g/g.Temperature programming is carried out to embodiment catalyst, 3 DEG C/min, enter feedstock oil at 150 DEG C.Continue to be warming up to 350 DEG C stablize 6 hours after start constant.Process conditions are: pressure 3.4MPa, air speed 2.0, temperature 350 DEG C, hydrogen to oil volume ratio 500.Evaluation result is in table 2.
The activity of embodiment 5 oxidized catalyst is investigated
Comparative example 1 catalyst is loaded in hydrogenation reactor, 150 DEG C are directly warming up to after the reactor that catalyst is housed imports hydrogen, enter sulfurized oil (mixture for navigate coal and carbon disulfide), rising to 350 DEG C subsequently carries out presulfurization, and constant temperature was adjusted to reaction condition after 6 hours.Feedstock oil and process conditions are with embodiment 4.Evaluation result is in table 2.
The activity of embodiment 6 ex situ presulfiding catalyst is investigated
Experiment completes on micro-reactor, and carrier gas is hydrogen.Temperature programming is carried out to comparative example 2 catalyst, 3 DEG C/min, enter feedstock oil at 90 DEG C.Continue to be warming up to 350 DEG C stablize 6 hours after start constant.Feedstock oil and process conditions are with embodiment 4.Evaluation result is in table 2.
The physico-chemical property of table 1 catalyst
| Catalyst is numbered | Total metal contents in soil, wt % | Specific area, m 2/g | Pore volume, mL/g | Average pore diameter, nm |
| Catalyst A | 28 | 240 | 0.45 | 7.5 |
| Catalyst B | 28 | 236 | 0.44 | 7.5 |
| Catalyst C | 28 | 220 | 0.44 | 8.0 |
| Catalyst D | 28 | 221 | 0.43 | 7.8 |
| Catalyst E | 28 | 173 | 0.32 | 7.4 |
| Catalyst F | 28 | 173 | 0.32 | 7.4 |
Note: the pore structure of catalyst is for changing into oxidation state post analysis gained.
The evaluation result of table 2 catalyst
| Catalyst is numbered | S，μg/g | N，μg/g |
| Catalyst A | 33.1 | <1.0 |
| Catalyst B | 21.7 | <1.0 |
| Catalyst C | 36.7 | <1.0 |
| Catalyst D | 45.9 | <1.0 |
| Catalyst E | 78.6 | 1.5 |
| Catalyst F | 72.4 | 1.5 |
As can be seen from Fig. 1 ~ 6 and table 1, table 2, active phase prepared by the inventive method is the active phase of highly active II class.When catalyst composition is identical with process conditions, the hydrogenation activity of sulfide type catalyst is apparently higher than the hydrogenation activity of oxidized catalyst and ex situ presulfiding catalyst.The preparation technology of catalyst is simple, good economy performance.Catalyst is the sulfide type catalyst of complete meaning, and start-up process is simple, avoids ex situ presulfiding catalyst initial temperature low, and heat release such as to concentrate at the generation of phenomenon.
Claims (15)
1. the preparation method of a sulfurized hydrogenation catalyst, comprise: adopt carrier predecessor and elementary sulfur, adjuvant kneading, shaping, dry, load hydrogenation active metals component, then heat-treat, obtain sulfurized hydrogenation catalyst, the addition of wherein said elementary sulfur is 100wt% ~ 250wt% that catalyst theory needs sulfur content, adjuvant is unsaturated hydro carbons or the mixture containing unsaturated hydro carbons, the boiling point of adjuvant is 150 ~ 370 DEG C, the addition of adjuvant counts 3% ~ 50% of carrier predecessor butt weight with unsaturated hydro carbons, described heat treated condition is as follows: at inert gas, under at least one gas in hydrogen exists, treatment temperature is 200 ~ 600 DEG C, processing time is 2 ~ 15 hours, described drying condition is as follows: 50 ~ 200 DEG C and baking temperature lower than the boiling point of adjuvant, dry 1 ~ 10 hour.
2. in accordance with the method for claim 1, it is characterized in that described drying condition is as follows: 120 ~ 180 DEG C and baking temperature lower than the boiling point of adjuvant, dry 2 ~ 5 hours.
3. in accordance with the method for claim 1, it is characterized in that described carrier be aluminium oxide, silica, titanium dioxide, zirconic one or more, carrier predecessor be carrier dehydration before compound.
4. in accordance with the method for claim 1, it is characterized in that adding in described kneading raw material in molecular sieve, bentonite, kaolin, sepiolite one or more.
5. in accordance with the method for claim 1, it is characterized in that: introduce in auxiliary agent P, B, Si, F, Mg, Zn when preparing carrier predecessor or when kneading one or more.
6. in accordance with the method for claim 1, it is characterized in that described adjuvant is unsaturated hydro carbons, comprise one or more in alkene, alkadienes, alkynes.
7. in accordance with the method for claim 1, it is characterized in that mixture that described adjuvant contains unsaturated hydro carbons is one or more in coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil, the concentration of unsaturated hydro carbons is 30v% ~ 60v%.
8. in accordance with the method for claim 1, it is characterized in that: when shaping, add in adhesive, extrusion aid one or more, described adhesive is one or more in nitric acid, hydrochloric acid, sulfuric acid, acetic acid, citric acid, and extrusion aid is one or more in sesbania powder, starch, talcum powder.
9. in accordance with the method for claim 1, it is characterized in that: with the weight of catalyst for benchmark, the content of hydrogenation active metals is 5wt% ~ 50wt%.
10. according to the method described in claim 1 or 9, it is characterized in that: described hydrogenation active metals is one or more in group VIB, group VIII metal, group VIB metal is Mo and/or W, and group VIII metal is Ni and/or Co.
11. in accordance with the method for claim 10, it is characterized in that: with the weight of catalyst for benchmark, and the content of group VIB metal is 15% ~ 30%, and the content of group VIII metal is 1% ~ 6%.
12. in accordance with the method for claim 1, it is characterized in that: the method for described load hydrogenation active metals component adopts kneading method or infusion process.
13. in accordance with the method for claim 12, it is characterized in that described infusion process first prepares the maceration extract containing hydrogenation active metals, then the dry support after shaping with above-mentioned impregnation fluid, drying is needed after dipping, drying condition is as follows: 50 ~ 200 DEG C and baking temperature lower than the boiling point of adjuvant, dry 1 ~ 10 hour.
14. in accordance with the method for claim 12, it is characterized in that described kneading method is added in the mixture of carrier predecessor, elementary sulfur and adjuvant with the form of solid or the aqueous solution by the compound containing hydrogenation active metals component to carry out kneading, then through shaping and dry.
15. in accordance with the method for claim 1, it is characterized in that described heat treatment carries out under at least one gas in inert gas, hydrogen exists, adopt Fractional Heat-treatment, specific as follows: 200 ~ 280 DEG C of constant temperature process 0 ~ 5 hour, then 290 ~ 350 DEG C of constant temperature process 1 ~ 5 hour, finally 360 ~ 600 DEG C of constant temperature process 1 ~ 5 hour.
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| CN106732666B (en) * | 2015-11-20 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of one-time formed macropore sulfurized hydrogenation catalyst |
| CN106946807B (en) * | 2016-01-07 | 2020-05-19 | 中国石油化工股份有限公司 | Hydrotreating catalyst intermediate, hydrotreating catalyst and preparation method thereof |
| CN106944125B (en) * | 2016-01-07 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN108067256B (en) * | 2016-11-15 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
| CN111468142A (en) * | 2020-04-08 | 2020-07-31 | 中国石油天然气股份有限公司 | Co-Mo-S catalyst and preparation method thereof |
| CN115505425A (en) * | 2022-09-19 | 2022-12-23 | 连云港鹏辰特种新材料有限公司 | Preparation method of high-boiling-point high-purity solvent oil for hydrogen peroxide production |
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