阅读说明：本技术 用于循环工作液再生的催化剂及其制备方法以及循环工作液的再生方法 (Regeneration method for regenerated catalyst of cycle working fluid and preparation method thereof and cycle working fluid ) 是由 刘碧波 谢正求 于涛 刘瑶 于 2019-08-26 设计创作，主要内容包括：本发明涉及一种用于循环工作液再生的催化剂及其制备方法以及循环工作液的再生方法,该催化剂含有含铝载体、氧化钛、氧化镁和第VIB族、VIIB族的过渡金属M氧化物；相对于10-98重量％的含铝载体,氧化钛的含量为0.1-30重量％,氧化镁的含量为1.0-50重量％,第VIB族、VIIB族的过渡金属M氧化物的含量为0.1-10重量％；所述含铝载体为Al<Sub>2</Sub>O<Sub>3</Sub>,本发明还公开了采用所述催化剂对蒽醌法生产过氧化氢工艺中循环工作液进行再生的方法。采用本发明的催化剂对蒽醌法生产过氧化氢工艺过程中的工作液进行再生,能获得更高的蒽酮型、羟基蒽酮、四氢蒽醌环氧化物和四氢-2-烷基蒽醌化合物转化率,降低循环工作液中降解物的累积,提高工作液的循环利用效率。(The present invention relates to a kind of regeneration method for regenerated catalyst of cycle working fluid and preparation method thereof and cycle working fluid, which contains the transition metal M oxide containing alumina supporter, titanium oxide, magnesia and group VIB, VIIB race；Relative to the alumina supporter that contains of 10-98 weight %, the content of titanium oxide is 0.1-30 weight %, and the content of magnesia is 1.0-50 weight %, and group VIB, the content of transition metal M oxide of VIIB race are 0.1-10 weight %；The alumina supporter that contains is Al 2 O 3 , the invention also discloses carry out regeneration method to cycle working fluid in process for prepairng hydrogen peroxide by anthraquinone technique using the catalyst.Working solution in process for prepairng hydrogen peroxide by anthraquinone technical process is regenerated using catalyst of the invention, higher anthrone type, hydroxyl anthrone, tetrahydro-anthraquinone epoxides and tetrahydro -2- alkylanthraquinone compounds conversion ratio can be obtained, the accumulation of degradation product in cycle working fluid is reduced, that improves working solution recycles efficiency.)

1. a kind of regenerated catalyst of cycle working fluid for process for prepairng hydrogen peroxide by anthraquinone technique, which is characterized in that this is urged Agent contain containing alumina supporter, titanium oxide, magnesia and metal M oxide；In terms of butt and with the total weight of the catalyst On the basis of, the content containing alumina supporter is 10-98 weight %, and the content of the titanium oxide is 0.1-30 weight %, the oxygen The content for changing magnesium is 1.0-50 weight %, and the content of the oxide of the metal M is 0.1-10 weight %, wherein the metal M For group VIB and/or the transition metal of VIIB race；

The catalyst is bar shaped catalyst, cylinder shape catalyst, ring catalyst, Clover-shaped catalyzer, quatrefoil catalysis One or more of agent, honeycomb-shaped catalyst and butterfly catalyst.

2. catalyst according to claim 1, wherein the alumina supporter that contains is aluminium oxide and/or boehmite；With dry Base meter and on the basis of the total weight of the catalyst, the content of aluminium oxide are 30-95 weight %, and the content of titanium oxide is 1-20 Weight %, the content of magnesia are 5-20 weight %, and the content of the oxide of the metal M is 0.2-5 weight %.

3. catalyst according to claim 1, wherein the metal M includes one of tungsten, molybdenum, chromium and manganese or a variety of.

4. the method for preparing catalyst described in any one of claim 1-3, which is characterized in that this method includes following step It is rapid:

(a) described the first mixing will be carried out containing alumina supporter, the source metal M, magnesium source, titanium source, deionized water and inorganic adhesive, obtained Shaping of catalyst precursor；

(b) shaping of catalyst precursor obtained in step (a) is subjected to extruded moulding, and after being dried and roasting, obtained To the catalyst.

5. the preparation method according to claim 4, wherein the first mixing described in step (a) includes: to carry described containing aluminium The titanium source mixing is added after body, the source metal M, magnesium source and inorganic adhesive mixing.

6. the preparation method according to claim 4, wherein relative to described in 100g contain alumina supporter, the use in the source the metal M Amount is 0.1~1g, and the dosage in the magnesium source is 1~80g, and the dosage of the titanium source is 1~60g, the use of the inorganic adhesive Amount is 0.005~20g；

The inorganic binder contains the aqueous solution of nitric acid of 0.5-20 weight % and the polyalcohol of 0.5-10 weight %, described polynary Alcohol is selected from the one or more of ethylene glycol, glycerine and 1,4-butanediol；

The titanium source includes titanyl compound, and the magnesium source includes one of the oxide of magnesium, the hydroxide of magnesium and magnesium salts Or it is a variety of；The source the metal M includes at least one of oxide and metal M salt of metal M.

7. preparation method according to claim 6, wherein this method include before step (b) before, will be in step (a) The mixture arrived carries out described second with inorganic oxide precursor body, expanding agent and extrusion aid and deionized water and mixes, and obtains institute State shaping of catalyst precursor；

The inorganic oxide precursor body is selected from least one of Aluminum sol, silica solution and waterglass；

The expanding agent is selected from sesbania powder, paraffin, stearic acid, glycerol, starch, polyethylene glycol, polyvinyl alcohol, polycyclic oxygen second One of alkane, polypropylene amine, methyl cellulose, cellulose, polymeric alcohol and graphite are a variety of；

The extrusion aid is selected from oxalic acid, tartaric acid, citric acid, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonium hydroxide, sodium hydroxide and hydrogen One of potassium oxide is a variety of；

It is counted by butt and by described containing on the basis of alumina supporter, the additional amount of the expanding agent is 1-10 weight %, the extrusion aid Additional amount be 0.5-10 weight %.

8. the preparation method according to claim 4, wherein the forming method includes: will be described obtained in step (b) Shaping of catalyst precursor extruded moulding in banded extruder, the catalyst are bar shaped catalyst.

9. preparation method according to claim 5, wherein the condition of the drying includes: that temperature is 80-200 DEG C, the time For 1-10h, the condition of the roasting includes: that temperature is 200-900 DEG C, time 0.5-10h.

10. a kind of regeneration method of the cycle working fluid of process for prepairng hydrogen peroxide by anthraquinone technique, which is characterized in that this method packet It includes: under working solution regeneration condition, catalyst described in any one of the cycle working fluid and claim 1-3 being connect Touching；Wherein, it is 20-120 DEG C, preferably 30-90 DEG C that the working solution regeneration condition, which includes: temperature,；Pressure is 0-1.5MPa, excellent It is selected as 0-1MPa.

Technical field

The invention belongs to hydrogen dioxide solution production by anthraquinone process technical fields, and in particular to one kind is urged for cycle working fluid to be regenerated The regeneration method of agent and preparation method thereof and cycle working fluid.

Background technique

Hydrogen peroxide (its aqueous solution is known as hydrogen peroxide), molecular formula H₂O₂, it is a kind of strong oxidizer, it can be with water with any Than mixing.H₂O₂In addition to being defended in food, medicine other than bleaching, chemicals synthesis and this three big field of environmental protection are widely used The application in the fields such as raw and electronics industry is also more and more.In particular with the development of titanium-silicon molecular sieve catalyst, H₂O₂As green Color oxidant is widely applied in the synthesis of many petrochemicals, as propylene oxide, benzenediol, caprolactam, Benzaldehyde and phenylacetaldehyde etc..

Anthraquinone is industrially to produce H at present₂O₂Main method.Process for prepairng hydrogen peroxide by anthraquinone is that working material is molten Solution forms working solution in organic solvent, and working solution is through over hydrogenation, oxidation and extraction, to obtain the technique mistake of hydrogen peroxide Journey, wherein working material can be alkyl-anthraquinone and/or alkyl hydrides anthraquinone, organic solvent be generally heavy aromatics and esters or The mixed solvent of higher alcohol.In hydrogenation process, in the presence of a hydrogenation catalyst, H is used₂Working material is hydrogenated, is generated corresponding Alkyl hydrogen anthraquinone and/or alkyl hydrides hydrogen anthraquinone, obtain hydride；In oxidation process, by hydride and oxygen or sky Gas contact, generates hydrogen peroxide, while alkyl hydrogen anthraquinone and/or alkyl hydrides hydrogen anthraquinone are recovered to alkyl-anthraquinone and/or hydrogen Change alkyl-anthraquinone；In extraction process, hydrogen peroxide is extracted from oxidation solution with water, is recycled back to hydrogen after raffinate is post-treated Change process.

In the technical process of process for prepairng hydrogen peroxide by anthraquinone, some side reactions can occur in hydrogenation and oxidation process, Cause working material to be degraded, loses it and generate H₂O₂Ability, form useless inertia degradation product, such as formed octahydro hydrogen anthraquinone, Hydroxyl anthrone, anthrone, tetrahydro-anthraquinone epoxides etc., wherein anthrone is most important degradation product.The generation of degradation product not only makes Anthraquinone content in working solution is constantly reduced, and reduces H₂O₂Preparation efficiency, and cause the change of working solution physical property, such as table The decline of face tension, viscosity increase, and system resistance increases, and effective ingredient is lost, and eventually leading to hydrogen peroxide yield reduces, under quality Drop, increased production cost, be normally carried out technical process can not.Therefore, the regeneration of anthraquinone degradation products be always people concern and The emphasis of research.

Summary of the invention

The object of the present invention is to provide a kind of catalyst of highly efficient regeneration anthraquinone degradation products, can be to anthraquinone production peroxide The working solution changed in hydrogen technical process is regenerated, and that improves working solution recycles efficiency.

To achieve the goals above, disclosure first aspect provides a kind of following for process for prepairng hydrogen peroxide by anthraquinone technique The regenerated catalyst of ring working solution: the catalyst contain containing alumina supporter, titanium oxide, magnesia and metal M oxide；With butt It counts and on the basis of the total weight of the catalyst, the content containing alumina supporter is 10-98 weight %, and the titanium oxide contains Amount is 0.1-30 weight %, and the content of the magnesia is 1.0-50 weight %, and the content of the oxide of the metal M is 0.1- 10 weight %, wherein the metal M is the transition metal of group VIB and/or VIIB race；

The catalyst is bar shaped catalyst, cylinder shape catalyst, ring catalyst, Clover-shaped catalyzer, quatrefoil One or more of catalyst, honeycomb-shaped catalyst and butterfly catalyst.

Optionally, the alumina supporter that contains is aluminium oxide and/or boehmite；In terms of butt and with the total of the catalyst On the basis of weight, the content of aluminium oxide is 30-95 weight %, and the content of titanium oxide is 1-20 weight %, and the content of magnesia is 5-20 weight %, the content of the oxide of the metal M are 0.2-5 weight %.

Optionally, the metal M includes one of tungsten, molybdenum, chromium and manganese or a variety of.

Disclosure second aspect: it provides the preparation method of catalyst disclosed in disclosure first aspect: (a) described will contain aluminium Carrier, the source metal M, magnesium source, titanium source, deionized water and inorganic adhesive carry out the first mixing, obtain shaping of catalyst precursor；

(b) shaping of catalyst precursor obtained in step (a) is subjected to extrusion forming, and is dried and roasts Afterwards, the catalyst is obtained.

Optionally, the first mixing described in step (a) includes: by described containing alumina supporter, the source metal M, magnesium source and inorganic viscous Connect agent add after mixing the titanium source be uniformly mixed.

Optionally, relative to alumina supporter is contained described in 100g, the dosage in the source the metal M is 0.1~1g, the use in the magnesium source Amount is 1~80g, and the dosage of the titanium source is 1~60g, and the dosage of the inorganic adhesive is 0.005~20g；

The inorganic binder contains the aqueous solution of nitric acid of 0.5-20 weight % and the polyalcohol of 0.5-10 weight %, described Polyalcohol is selected from the one or more of ethylene glycol, glycerine and 1,4-butanediol；

The titanium source includes titanyl compound, and the magnesium source includes in the hydroxide and magnesium salts of the oxide of magnesium, magnesium It is one or more；At least one of oxide and metal M salt of metal M.

Optionally, before this method includes before step (b), before mixture obtained in step (a) and inorganic oxide It drives body, expanding agent and extrusion aid and deionized water carries out second mixing, obtain the shaping of catalyst precursor；

The inorganic oxide precursor body is selected from least one of Aluminum sol, silica solution and waterglass；

The expanding agent is selected from sesbania powder, paraffin, stearic acid, glycerol, starch, polyethylene glycol, polyvinyl alcohol, polycyclic oxygen One of ethane, polypropylene amine, methyl cellulose, cellulose, polymeric alcohol and graphite are a variety of；

The extrusion aid is selected from oxalic acid, tartaric acid, citric acid, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonium hydroxide, sodium hydroxide With one of potassium hydroxide or a variety of；

It is counted by butt and by described containing on the basis of alumina supporter, the additional amount of the expanding agent is 1-10 weight %, described to help The additional amount for squeezing agent is 0.5-10 weight %.

Optionally, the forming method include: by shaping of catalyst precursor obtained in step (b) in banded extruder Extruded moulding, the catalyst are bar shaped catalyst.

Optionally, it is 80-200 DEG C, time 1-10h that the condition of the drying, which includes: temperature, the condition packet of the roasting Include: temperature is 200-900 DEG C, time 0.5-10h.

The disclosure third aspect provides a kind of regeneration method of the cycle working fluid of process for prepairng hydrogen peroxide by anthraquinone technique, This method comprises: will be urged described in any one of the cycle working fluid and claim 1-4 under working solution regeneration condition Agent contact；

Optionally, it is 20-120 DEG C, preferably 30-90 DEG C that the working solution regeneration condition, which includes: temperature,；Pressure is 0- 1.5MPa, preferably 0-1MPa.

Through the above technical solutions, the catalyst of the disclosure contains titanium dioxide and containing alumina supporter, catalyst can be improved Activity and anthrone type compound transform into the catalytic conversion in the reaction of anthraquinone type compound；The catalyst system of the disclosure Preparation Method can be improved the intensity of finished catalyst using sol adhesive；It can be to anthraquinone life using the catalyst of the disclosure Working solution during production hydrogen peroxide process is regenerated, and higher anthrone type, hydroxyl anthrone, tetrahydro-anthraquinone epoxy can be obtained Compound and tetrahydro -2- alkylanthraquinone compounds conversion ratio reduce the accumulation of degradation product in cycle working fluid, improve following for working solution Ring utilization efficiency.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that specific reality described herein The mode of applying is merely to illustrate and explain the present invention.

According to the disclosure in a first aspect, providing a kind of cycle working fluid regeneration for process for prepairng hydrogen peroxide by anthraquinone technique Catalyst, the catalyst contain containing alumina supporter, titanium oxide, magnesia and metal M oxide；It is urged in terms of butt and with described On the basis of the total weight of agent, the content containing alumina supporter is 10-98 weight %, and the content of the titanium oxide is 0.1-30 weight % is measured, the content of the magnesia is 1.0-50 weight %, and the content of the oxide of the metal M is 0.1-10 weight %, In, the metal M is the transition metal of group VIB and/or VIIB race.

Preferably, it is counted by butt and on the basis of the total weight of the catalyst, the content of aluminium oxide is 30-95 weight % is measured, the content of titanium oxide is 1-20 weight %, and the content of magnesia is 5-20 weight %, and the oxide of the metal M contains Amount is 0.2-5 weight %.

It is further preferred that catalyst can be bar shaped catalyst, cylinder shape catalyst, ring catalyst, cloverleaf pattern One or more of catalyst, quatrefoil catalyst, honeycomb-shaped catalyst and butterfly catalyst.

The catalyst provided using disclosure first aspect is to the working solution in process for prepairng hydrogen peroxide by anthraquinone technical process It is regenerated, higher anthrone type compound ratio transformation can be obtained, the accumulation for reducing anthrone type compound in cycle working fluid contains Amount, that improves working solution recycles efficiency.Also, catalyst according to the invention has longer service life, can be effective Ground extends the replacement cycle of catalyst, reduces operating cost, while reducing since working solution loses caused by more catalyst changeout Amount.

According to the disclosure, the carrier can be common heat-resistant inorganic oxide.Preferably, the carrier contains oxidation Aluminium can be further improved urging when being used as the catalyst by the reaction that anthrone type compound transforms into anthraquinone type compound in this way Change activity.

According to the disclosure, the metal M is selected from the transition metal of group VIB and/or VIIB race, and the metal M can be At least one of manganese, chromium, molybdenum, tungsten, iron, chromium and nickel.It is used as from the catalyst is further increased by the conversion of anthrone type compound The angle of the catalytic activity of the catalyst of reaction as anthraquinone type compound is set out, the metal M be preferably tungsten, molybdenum, chromium and At least one of manganese.

According to disclosure second aspect, the preparation method of the catalyst of disclosure first aspect is provided, this method includes such as Lower step: (a) described will carry out the first mixing containing alumina supporter, the source metal M, magnesium source, titanium source, deionized water and inorganic adhesive, Obtain shaping of catalyst precursor；(b) shaping of catalyst precursor obtained in step (a) is subjected to extrusion forming, and carried out After dry and roasting, the catalyst is obtained.

Titanium oxide is added in the regenerated catalyst of cycle working fluid in process for prepairng hydrogen peroxide by anthraquinone technique in the present invention, can To improve the intensity of catalyst, and further increase the reaction for being used as and anthrone type compound being transformed into anthraquinone type compound Catalyst when catalytic activity.

According to the disclosure, titanium source, magnesium source and the source metal M in the disclosure are all made of the common substance in this field, in order to drop The cumulative amount of anthrone type compound in low circulation working solution, that improves working solution recycles efficiency, obtains higher anthrone Type compound ratio transformation, titanium source may include titanyl compound, for example, rutile-type and anatase-type titanium oxide, preferably sharp Titanium ore type titanium oxide；Magnesium source may include at least one of the oxide of magnesium, the hydroxide of magnesium and magnesium salts, for example, aoxidize Magnesium, magnesium hydroxide, magnesium nitrate；The source the metal M may include the oxide and metal M salt of metal M.

According in disclosed method, the dosage containing alumina supporter, the source metal M, magnesium source, titanium source and inorganic adhesive can be with Change in a big way, it is preferable that relative to the alumina supporter that contains of 100g, the dosage in the source metal M can be 0.1~1g, magnesium source Dosage can be 1~80g, the dosage of titanium source can be 1~60g, and the dosage of inorganic adhesive can be 0.005~20g.

According to the disclosure, in step (a), inorganic adhesive selects that well known to a person skilled in the art for the viscous of catalyst Agent is tied, can be the mixture of aqueous solution of nitric acid and polyalcohol, further, polyalcohol is selected from ethylene glycol, glycerine and Isosorbide-5-Nitrae- The one or more of butanediol.In order to make the oxide powder particle containing alumina supporter, magnesia and metal M be bonded in one It rises, to improve intensity and the service life of composite catalyst, when preventing content of binder deficiency, it is difficult to form, cause leaving into Situation about will be crushed when type machine；And when avoiding binder amount excessive, catalyst precarsor softens tacky situation, it is preferable that this In disclosed method, inorganic binder can the aqueous solution of nitric acid containing 0.5-20 weight % and 0.5-10 weight % it is polynary Alcohol.

In disclosed method, shaping of catalyst precursor obtained in step (b) carry out extruded moulding, and be dried and After roasting, the catalyst is obtained.The state of catalyst is not required particularly in the disclosure, further, in order to make to urge Agent can be placed in fixed bed reactors or moving-burden bed reactor, it is preferable that catalyst can be bar shaped catalyst.

Preferably, using drying means commonly used in the art, the condition of the drying may include: that temperature is 80-200 DEG C, time 1-10h；Furthermore the method for roasting common using this field, the condition of the roasting may include: that temperature is 200- 900 DEG C, time 0.5-10h.

In a kind of preferred embodiment of the disclosure, the first mixing described in step (a) may include: by described containing aluminium Carrier, the source metal M, magnesium source, deionized water and inorganic adhesive add the titanium source after mixing and are uniformly mixed.At this In preferred embodiment, titanium source is added, the intensity of catalyst can be improved, and further increases and be used as anthrone type chemical combination Object transforms into the catalytic activity when catalyst of the reaction of anthraquinone type compound.

In a kind of preferred embodiment of the disclosure, carry out that expanding agent and/or extrusion aid can be added when the second mixing, For example, can by mixture obtained in step (a) and inorganic oxide precursor body and expanding agent, extrusion aid, deionized water into Row second mixing, obtains the shaping of catalyst precursor.

According to the disclosure, what inorganic oxide precursor body can be well known in the art can obtain inorganic oxide after baking The substance of object, inorganic oxide are resistant to the corrosion of strong acid, highly basic as inert substance, so that shaped granule be made to take out in lye It is unlikely to crush during mentioning, in order to further increase intensity and the service life of composite catalyst, inorganic oxide precursor body is preferred For at least one of Aluminum sol, silica solution and waterglass.

In order to facilitate the extrusion molding of catalyst and the duct of increase catalyst, expanding agent can be added and/or help crowded Agent can be removed expanding agent and extrusion aid at high temperature in roasting process, and expanding agent and extrusion aid are those skilled in the art Member known to, it is preferable that expanding agent can for sesbania powder, paraffin, stearic acid, glycerol, starch, polyethylene glycol, polyvinyl alcohol, One of polyethylene oxide, polypropylene amine, methyl cellulose, cellulose, polymeric alcohol and graphite are a variety of；Extrusion aid can be One of oxalic acid, tartaric acid, citric acid, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonium hydroxide, sodium hydroxide and potassium hydroxide are a variety of.

In order to obtain higher anthrone type compound ratio transformation, the accumulation for reducing anthrone type compound in cycle working fluid contains Amount, that improves working solution recycles efficiency.The disclosure third aspect provides a kind of following for process for prepairng hydrogen peroxide by anthraquinone technique The regeneration method of ring working solution, this method comprises: under working solution regeneration condition, by the working solution and disclosure first aspect The catalyst of offer contacts, what working solution regeneration condition can be conventional for this field, and under preferable case, working solution regeneration condition can It can be 20-120 DEG C, preferably 30-90 DEG C to include: temperature；Pressure can be 0-1.5MPa, preferably 0-1MPa, with into One step improves the regenerated efficiency of working solution.

Other feature and advantage of the disclosure will be described in detail in subsequent specific implementation part.

In the following embodiments and comparative example of the disclosure, it is all made of common commercially available experimental drug.