CN108298503B - A kind of technique of efficient production hydrogen peroxide - Google Patents
A kind of technique of efficient production hydrogen peroxide Download PDFInfo
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Abstract
The invention belongs to chemical fields, more particularly to a kind of technique of efficiently production hydrogen peroxide, using heavy aromatics, trioctyl phosphate as solvent, 2- ethyl hydrazine is that working material is prepared to obtain working solution, working solution is under the catalytic action of graphene/alumina load palladium catalyst, hydrogenation is carried out with hydrogen, reaction temperature, reaction pressure and the working solution sprinkle density by controlling hydriding process make 2- ethyl tetrahydro-anthraquinone and the content ratio of 2- ethyl hydrazine in reaction solution maintain (4~5): in the range of (5~6).Compared with traditional handicraft, which can make hydrogenation efficiency improve 32%, production capacity can synchronize raising 32%, and the usage amount of catalyst can reduce 60% or more, achieve significant progress under same degree of hydrogenation.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of technique of efficiently production hydrogen peroxide.
Background technique
The industrial process of hydrogen peroxide is predominantly anthraquinone, is with 2- ethyl hydrazine (EAQ) for working material, with weight
Aromatic hydrocarbons (Ar), trioctyl phosphate (TOP) or other groups are divided into working solvent and are made into working solution, extract through over hydrogenation, oxidation, pure water
With working solution post-processing etc. processes, obtain certain density hydrogen peroxide product.
In the hydrogenation process of hydrogen dioxide solution production by anthraquinone process, hydrogenation process is very important production unit, directly affects
The quality level and product quality of hydrogenation efficiency, working solution.Anthracene in hydrogenation, under palladium catalyst in hydrogen and working solution
Quinone reaction, generates 2- ethyl hydrogen anthraquinone and 2- ethyl tetrahydro hydrogen anthraquinone, then after air oxidation reaction, 2- ethyl hydrogen anthraquinone and 2-
Ethyl tetrahydro hydrogen anthraquinone reduction generates hydrogen peroxide at 2- ethyl hydrazine and 2- ethyl tetrahydro-anthraquinone, and whole system is continuously closed
Circulation production.Reaction temperature is generally 40~75 DEG C, and reaction pressure is generally 0.2~0.4MPa.In the technology, working solution is to 2-
Ethyl hydrazine and the solubility of 2- ethyl tetrahydro-anthraquinone is not high, causes hydrogenation efficiency not high, production capacity is low.Therefore, how to mention
High anthraquinone is the technical issues of the concentration of working solution is current urgent need to resolve.
And it is directed to the technical problem, existing solution in working solution generally by introducing third component solvent, such as
Chinese patent application CN103588177A, inventor introduce 2- methylcyclohexyl acetate on the basis of original working solution,
Achieve the purpose that the solubility for improving anthraquinone and hydrogen anthraquinone, this method can make the solubility of general anthraquinone in working solution reach 180~
200g/L, but the unit volume working solution productivity ratio prior art improves about 35%；Such as Chinese patent application CN105819402A,
A kind of Novel work liquid system is inventor provided, the percent by volume of solvent each component in working solution are as follows: trimethylbenzene 60~
80%, trioctyl phosphate 0.5~25%, tetrabutyl urea 0.5~25%, 2- methylcyclohexyl acetate 0.5~25%, the work
Liquid can make the total anthraquinones content in working solution reach 140~200g/L, and hydrogen effect can reach 12~15g/L, improve production energy
Power.But the above method is due to introducing more organic solvents, and leading to product, there are more organic impurities and technique are immature
Property, secondly, palladium catalyst catalysis is all made of in existing hydrogen peroxide production process, wherein multi-purpose alumina load, but common oxygen
There is activity and selectivity difference in the catalyst for changing aluminium load.
Therefore, it is necessary to provide a kind of hydrogenation efficiency and the high technique of production capacity to meet needed for reality.
Summary of the invention
The present invention is intended to provide a kind of technique of efficiently production hydrogen peroxide, compared with traditional handicraft, the technique is same
Degree of hydrogenation under, can make hydrogenation efficiency improve 32%, production capacity can synchronize raising 32%, and greatly reduce the use of catalyst
Amount.
In order to achieve the above object, the invention adopts the following technical scheme: one kind efficiently produces the technique of hydrogen peroxide, with
Heavy aromatics, trioctyl phosphate are solvent, and 2- ethyl hydrazine is that working material is prepared to obtain working solution, and working solution is in graphene/oxygen
Under the catalytic action for changing aluminium loaded palladium catalyst, hydrogenation is carried out with hydrogen, by the reaction temperature for controlling hydriding process
Degree, reaction pressure and working solution sprinkle density maintain the content of 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine ratio in reaction solution
In (4~5): in the range of (5~6).
Further, 2- ethyl tetrahydro-anthraquinone and the content ratio of 2- ethyl hydrazine are 4.5:5.5.
Further, the inlet temperature is 45~50 DEG C.
Further, the reaction pressure is 0.25~0.35MPa.
Further, the working solution sprinkle density is 95~110m3/ (m2h).
Further, the graphene/alumina load palladium catalyst is made by following steps:
S1, carrier preparation: take boehmite be added reactor in, into reactor addition boehmite total amount 30~
0.1~0.3 times of boehmite total amount amount is added in the deionized water of 70 times of amounts, 80~85 DEG C of 10~30min of stirred in water bath
Concentrated nitric acid continues 3~5h of stirring；By admixed graphite alkene ultrasonic disperse in dehydrated alcohol, it is then added in above-mentioned reactor,
Continue 3~10h of stirring, age overnight is dried in baking oven, grinding, be placed in tube furnace, under the atmosphere of nitrogen, with 10 DEG C/
The heating rate of min rises to 500 DEG C, roasts 2~4h to get graphene/alumina composite carrier；
S2, above-mentioned carrier being impregnated into 20~40min in green palladium acid solution, deionized water is washed to neutrality, and 100~200
DEG C dry 8~12h, 300~500 DEG C of 1~3h of roasting to get.
Further, the admixed graphite alkene is made of single-layer graphene and bilayer graphene, wherein single-layer graphene
Content is not less than 50%.
Further, the volume ratio of the heavy aromatics, trioctyl phosphate and 2- ethyl hydrazine is (3.0~3.2): 1.
Further, the initial concentration of 2- ethyl hydrazine is 170-180g/L in the working solution.
Further, the technique is further comprising the steps of:
A it) aoxidizes: the acid content of hydride being adjusted to 3mgH3PO4/L~5mgH3PO4/L with phosphoric acid solution, is passed through pressure
Contracting air carries out oxidation reaction, obtains oxidation solution；
B it) extracts: acid pure water being added into oxidation solution and is extracted, it is purified to obtain hydrogen peroxide product, raffinate warp
Coarse separation is detached from free water and free hydrogen peroxide；
C) post-process: by raffinate by drying tower (inside having solution of potassium carbonate) dehydration, neutralizing acid, peroxynitrite decomposition hydrogen,
After regeneration purification, raffinate is used as cycle industrial liquid.
Inventor is in long-term production process, it has unexpectedly been found that, by adjusting reaction temperature, pressure and working solution spray
The control of the ratio of 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine is in (4~5) in density domination working solution: in the range of (5~6),
The solubility of general anthraquinone in working solution can be made to improve, can reach 185g/L, meanwhile, under same degree of hydrogenation, hydrogen effect
It can be improved 32%, production capacity can synchronize raising 32%, and unexpected technical results have been achieved.
Secondly, aluminium oxide as between carrier and active constituent have high forces, and inventors have found that by aluminium oxide with
Single-layer graphene is compound, and the specific surface area of catalyst can be improved, and forms macropore inside aluminium oxide and guarantee to aoxidize
The intensity of aluminium, can inhibit the degradation of anthraquinone, and improve the selectivity of catalyst.More it is surprising that being added on this basis
Bilayer graphene, and guarantee that the content of single-layer graphene must be remarkably improved and urge not less than 50% catalyst being prepared
The dosage of the activity and selectivity of agent, catalyst can greatly reduce, and for producing 10 tons of hydrogen peroxide (27.5%), need
Using 10 tons or so of common palladium series catalyst, and 3.5 tons are only needed using catalyst of the present invention.
The invention has the following advantages that
The present invention provides a kind of techniques of new production hydrogen peroxide, and compared with traditional handicraft, the technique is in same hydrogen
Under change degree, hydrogenation efficiency can be made to improve 32%, production capacity can synchronize raising 32%, and the usage amount of catalyst can reduce 60%
More than, achieve significant progress.
Specific embodiment
The specific embodiment of form by the following examples makees further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
Single-layer graphene is bought in Beijing Deco Dao Jin Science and Technology Ltd., and bilayer graphene is purchased from Nanjing Xian Feng nanometers of material
Expect Science and Technology Ltd..
Embodiment 1, graphene/alumina load palladium catalyst preparation
S1, carrier preparation: it takes boehmite to be added in reactor, 70 times of boehmite total amount is added into reactor
The deionized water of amount, 80 DEG C of stirred in water bath 30min are added the concentrated nitric acid of 0.13 times of boehmite total amount amount, continue to stir
5h；It by admixed graphite alkene ultrasonic disperse in dehydrated alcohol, is then added in above-mentioned reactor, continues to stir 6h, aging
Night dries in baking oven, and grinding is placed in tube furnace, under the atmosphere of nitrogen, rises to 500 with the heating rate of 10 DEG C/min
DEG C, 4h is roasted to get graphene/alumina composite carrier；
S2, above-mentioned carrier being impregnated into 30min in green palladium acid solution, deionized water is washed to neutrality, 200 DEG C of dry 12h,
500 DEG C of roasting 3h are to get wherein admixed graphite alkene is made of 55% single-layer graphene and 45% bilayer graphene.
Embodiment 2, the preparation of alumina load palladium catalyst
Embodiment 2 the difference from embodiment 1 is that: be added without graphene, remaining parameter is same as Example 1.
Embodiment 3, the preparation of alumina load palladium catalyst
Embodiment 3 the difference from embodiment 1 is that: admixed graphite alkene be single-layer graphene, remaining parameter and 1 phase of embodiment
Together.
Embodiment 4, a kind of technique of efficiently production hydrogen peroxide
A it) hydrogenates: taking heavy aromatics and trioctyl phosphate according to the volume ratio of 3:1, be made into work using 2- ethyl hydrazine as carrier
Liquid, the initial concentration of 2- ethyl hydrazine is 170g/L in working solution, working solution pump is continuously pumped into hydrogenation tower, while continuously
Hydrogen is passed through into hydrogenation tower, control reaction temperature is 48~50 DEG C, and reaction pressure is 0.25~0.35MPa, working solution spray
Density is 90~110m3/ (m2h), and controlling 2- ethyl tetrahydro-anthraquinone and the content ratio of 2- ethyl hydrazine in reaction solution is 4.5:
5.5, under the catalysis of the graphene that embodiment 1 is prepared/alumina load palladium catalyst, continuous hydrogenation reaction is carried out, is obtained
To hydride；
B it) aoxidizes: the acid content of hydride being adjusted to 4mgH with phosphoric acid solution3PO4/ L, using hydrogenation liquid pump by hydride
It is pumped into oxidizing tower from the hydrogenated liquid cooler of hydride medial launder, is passed through compressed air, carry out oxidation reaction, separation oxidation
Liquid is sent into oxidation solution medial launder；
C it) extracts: phosphoric acid solution being added in pure water and is allowed to acid content and reaches 0.1g/l, among oxidation solution autoxidation liquid
Slot is pumped into extraction tower, separated from the water through working solution extracted (raffinate), into postprocessing working procedures；Extract liquor is from extraction tower
It is purified into purifying column, purified hydrogen peroxide is flowed out from tower lower part, and into decontaminating separator, further separation can wherein
Can entrainment heavy aromatics, subsequently into finished product medial launder, the heavy aromatics being passed through in air scavenging finished product into the slot then will be at
Product are put into finished product reserve tank, can pack and store；
D) post-process: by raffinate by drying tower (inside having solution of potassium carbonate) dehydration, neutralizing acid, peroxynitrite decomposition hydrogen,
After regeneration purification, raffinate is used as cycle industrial liquid.
Embodiment 5, a kind of technique of efficiently production hydrogen peroxide
Embodiment 5 and the difference of embodiment 4 be, controls containing for 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Amount ratio is 4:6, remaining parameter is same as Example 4.
Embodiment 6, a kind of technique of efficiently production hydrogen peroxide
Embodiment 6 and the difference of embodiment 4 be, controls containing for 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Amount ratio is 5:5, remaining parameter is same as Example 4.
Embodiment 7, a kind of technique of efficiently production hydrogen peroxide
Embodiment 7 and the difference of embodiment 4 be, controls containing for 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Amount ratio is 5.5:4.5, remaining parameter is same as Example 4.
Embodiment 8, a kind of technique of efficiently production hydrogen peroxide
Embodiment 8 and the difference of embodiment 4 be, controls containing for 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Amount ratio is 3:7, remaining parameter is same as Example 4.
Embodiment 9, a kind of technique of efficiently production hydrogen peroxide
The difference of embodiment 9 and embodiment 4 is to control containing for 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Amount ratio is 3.5:6.5, remaining parameter is same as Example 4.
Embodiment 10, a kind of technique of efficiently production hydrogen peroxide
Embodiment 10 and the difference of embodiment 4 are, control 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Content ratio is 3:7, remaining parameter is same as Example 4.
Embodiment 11, a kind of technique of efficiently production hydrogen peroxide
Embodiment 11 and the difference of embodiment 4 are, control 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in reaction solution
Content ratio is 2:8, remaining parameter is same as Example 4.
Embodiment 12, a kind of technique of efficiently production hydrogen peroxide
Embodiment 12 and the difference of embodiment 4 are that catalyst is the alumina load palladium chtalyst that embodiment 2 is prepared
Agent, remaining parameter are same as Example 4.
Embodiment 13, a kind of technique of efficiently production hydrogen peroxide
Embodiment 13 and the difference of embodiment 4 are that catalyst is the alumina load palladium chtalyst that embodiment 3 is prepared
Agent, remaining parameter are same as Example 2.
Test one, performance evaluation
Hydrogen peroxide is produced according to the technique of embodiment 4~13, in terms of 10 tons of production capacity (concentration 27.5%), calculating is urged
The solubility of general anthraquinone in agent dosage, hydrogenation efficiency and each technique hydrogenation procedure, the results are shown in Table 1.
1 various processes performance evaluation of table
| Technique | General anthraquinone solubility | Hydrogenation efficiency | Catalyst amount |
| Embodiment 4 | 185g/L | 15.5g/L | 3.5 ton |
| Embodiment 5 | 180g/L | 14.8g/L | 3.5 ton |
| Embodiment 6 | 175/L | 14.8g/L | 3.5 ton |
| Embodiment 7 | 172/L | 14.5g/L | 3.5 ton |
| Embodiment 8 | 160g/L | 14.0g/L | 3.5 ton |
| Embodiment 9 | 151g/L | 13.6g/L | 3.5 ton |
| Embodiment 10 | 146g/L | 13.2g/L | 3.5 ton |
| Embodiment 11 | 141g/L | 12.8g/L | 3.5 ton |
| Embodiment 12 | 162g/L | 10.3g/L | 10.2 tons |
| Embodiment 13 | 165g/L | 11.5g/L | 8.3 ton |
As seen from the above table, when in hydrogenation the ratio of 2- ethyl tetrahydro-anthraquinone and 2- ethyl hydrazine in (4~5): (5~
6) when in the range of, the solubility of general anthraquinone can achieve 172g/L or more, if when ratio control is in 4.5:5.5, general anthraquinone
Solubility can achieve 185g/L.Secondly, traditional alumina load need to be added in terms of 10 tons of production capacity (concentration 27.5%)
10 tons of palladium catalyst, graphene/alumina load palladium catalyst of the present invention is added and only needs 3.5 tons.In addition, embodiment 12
Hydrogenation efficiency and anthraquinone solubility with 13 also decrease compared with Example 4, this explanation, new catalytic provided by the invention
Agent can be improved the activity and selectivity of catalyst, and side reaction is reduced, and degree of hydrogenation improves, and greatly save the use of catalyst
Amount, reduces production cost.
The influence of test two, different graphene ratios to catalyst performance
On the basis of embodiment 1, the dosage of single-layer graphene is arranged according to the form below 2, and each group catalyst is prepared, to produce
10 tons of meters (27.5%) of energy, produce according to technique described in embodiment 4, calculate the dosage of each group catalyst in production process, as a result
As shown in table 3 below.
2 single-layer graphene dosage of table
| Technique | Single-layer graphene dosage |
| ① | 55% |
| ② | 50% |
| ③ | 45% |
| ④ | 40% |
| ⑤ | 35% |
3 catalyst amount of table
| Technique | Catalyst amount |
| ① | 3.5 ton |
| ② | 5.3 ton |
| ③ | 6.0 ton |
| ④ | 6.5 ton |
| ⑤ | 7.2 ton |
By upper table 3 it is found that the single-layer graphene that different proportion is added in preparing palladium catalyst imitates the entirety of catalyst
Fruit has large effect, and optimal additional amount is 55%, at this point, the dosage of catalyst greatly reduces.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (7)
1. a kind of technique of efficiently production hydrogen peroxide, using heavy aromatics, trioctyl phosphate as solvent, 2- ethyl hydrazine is work load
Body is prepared to obtain working solution, which is characterized in that working solution under the catalytic action of graphene/alumina load palladium catalyst, with
Hydrogen carries out hydrogenation, and reaction temperature, reaction pressure and the working solution sprinkle density by controlling hydriding process make
2- ethyl tetrahydro-anthraquinone and the content ratio of 2- ethyl hydrazine maintain 4.5:5.5, the graphene/alumina load in reaction solution
Palladium catalyst is made by following steps:
S1, carrier preparation: it takes boehmite to be added in reactor, 30~70 times of boehmite total amount is added into reactor
The dense nitre of 0.1~0.3 times of boehmite total amount amount is added in the deionized water of amount, 80~85 DEG C of 10~30min of stirred in water bath
Acid continues 3~5h of stirring；It by admixed graphite alkene ultrasonic disperse in dehydrated alcohol, is then added in above-mentioned reactor, continues
3~10h is stirred, age overnight is dried in baking oven, is ground, is placed in tube furnace, under the atmosphere of nitrogen, with 10 DEG C/min
Heating rate rise to 500 DEG C, roast 2~4h to get graphene/alumina composite carrier；
S2, above-mentioned carrier is impregnated into 20~40min in green palladium acid solution, deionized water is washed to neutrality, and 100~200 DEG C dry
Dry 8~12h, 300~500 DEG C of 1~3h of roasting to get；
Wherein, the admixed graphite alkene is made of single-layer graphene and bilayer graphene, and wherein the content of single-layer graphene is not low
In 50%.
2. technique as described in claim 1, which is characterized in that the reaction temperature is 45~50 DEG C.
3. technique as described in claim 1, which is characterized in that the reaction pressure is 0.25~0.35MPa.
4. technique as described in claim 1, which is characterized in that the working solution sprinkle density is 95~110m3/(m2·h)。
5. technique as described in claim 1, which is characterized in that the heavy aromatics and trioctyl phosphate volume ratio be (3.0~
3.2): 1.
6. technique as described in claim 1, which is characterized in that the initial concentration of 2- ethyl hydrazine is 170- in the working solution
180g/L。
7. technique as described in claim 1, which is characterized in that the technique is further comprising the steps of:
A it) aoxidizes: the acid content of hydride being adjusted to 3mgH with phosphoric acid solution3PO4/ L~5mgH3PO4/ L, is passed through compressed air
Oxidation reaction is carried out, oxidation solution is obtained；
B it) extracts: acid pure water being added into oxidation solution and is extracted, purified to obtain hydrogen peroxide product, raffinate is through coalescing
Separation is detached from free water and free hydrogen peroxide；
C it) post-processes: by raffinate after drying tower dehydration, neutralizing acid, peroxynitrite decomposition hydrogen, regeneration purification, raffinate conduct
Cycle industrial liquid uses.
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| CN1175931C (en) * | 2003-02-21 | 2004-11-17 | 福州大学 | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof |
| CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
| CN103663385B (en) * | 2012-09-21 | 2015-09-09 | 中国石油化工股份有限公司 | A kind of method and apparatus producing hydrogen peroxide |
| CN103769087A (en) * | 2012-10-17 | 2014-05-07 | 南京大学连云港高新技术研究院 | Supported palladium catalyst for production of hydrogen peroxide through anthraquinone hydrogenation method, and preparation method thereof |
| CN104401944A (en) * | 2014-10-29 | 2015-03-11 | 广西田东达盛化工科技有限公司 | Preparation process of high-purity hydrogen peroxide |
| CN106861691B (en) * | 2015-12-12 | 2019-10-11 | 中国科学院大连化学物理研究所 | A kind of preparation of hydrogenation catalyst and hydrogenation catalyst and application |
| CN106179506B (en) * | 2016-06-24 | 2019-06-18 | 中国科学院福建物质结构研究所 | A kind of support type palladium-based catalyst and its preparation method and application |
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Denomination of invention: An Efficient Process for Producing Hydrogen Peroxide Effective date of registration: 20230922 Granted publication date: 20190329 Pledgee: China Guangfa Bank Bank Co.,Ltd. Yunfu Sub branch Pledgor: GUANGDONG XINGUOYUAN ENERGY CO.,LTD. Registration number: Y2023980058424 |