CN103252233B - Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst - Google Patents

Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst Download PDF

Info

Publication number
CN103252233B
CN103252233B CN201310135495.4A CN201310135495A CN103252233B CN 103252233 B CN103252233 B CN 103252233B CN 201310135495 A CN201310135495 A CN 201310135495A CN 103252233 B CN103252233 B CN 103252233B
Authority
CN
China
Prior art keywords
hydrolyst
mno
tio
sio
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310135495.4A
Other languages
Chinese (zh)
Other versions
CN103252233A (en
Inventor
周中平
马名章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi brothers Pharmaceutical Co., Ltd.
Original Assignee
BROTHER SCIENCE AND TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BROTHER SCIENCE AND TECHNOLOGY Co Ltd filed Critical BROTHER SCIENCE AND TECHNOLOGY Co Ltd
Priority to CN201310135495.4A priority Critical patent/CN103252233B/en
Publication of CN103252233A publication Critical patent/CN103252233A/en
Application granted granted Critical
Publication of CN103252233B publication Critical patent/CN103252233B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention belongs to the technical field of catalysis, and relates to a hydrolysis catalyst. The catalyst consists of a MnO2 (manganese dioxide) active part and a TiO2-SiO2 (titanium dioxide-silicon dioxide) carrier part containing SiO2, and solves the problems of the existing hydrolysis catalyst that the consumption is large, the reaction temperature is high, the catalyzing efficiency is low, and the cycling application stability is poor. The invention further provides a method for preparing the hydrolysis catalyst and a method for preparing nictinamide by utilizing the hydrolysis catalyst.

Description

A kind of hydrolyst and preparation method thereof and the method for the preparation of niacinamide
Technical field
The invention belongs to catalysis technical field, relate to a kind of hydrolyst and prepare the method for hydrolyst, due to the catalyst that hydrolyst of the present invention can be for nicotinonitrile hydrolysis niacinamide, present invention also offers a kind of preparation method of niacinamide.
Background technology
Industrial method of being produced niacinamide by catalyzing hydrolysis nicotinonitrile, selected catalyst is primarily of acid, alkali and some water-insoluble catalyst, such as NiO, MgO, MnO 2deng, there is Patent data to show, utilize KMnO 4with MnSO 4at the MnO that redox reaction is produced 2for catalyst, the productive rate that niacinamide is produced in the hydrolysis of catalysis nicotinonitrile reaches about 80%, and visible manganese dioxide has good catalysis potential.
In addition research display is had, with MnO 2for the reaction system of catalyst, ubiquity consumption is large, and reaction temperature is higher, and catalytic efficiency is low, recycles the problems such as poor stability.
Summary of the invention
First technical problem to be solved by this invention is MnO 2catalyst (being such as converted into the hydrolysis of niacinamide by nicotinonitrile) ubiquity consumption when participating in hydrolysis is large, and reaction temperature is higher, and catalytic efficiency is low, recycles the problem of poor stability, and provides a kind of hydrolyst.
A kind of hydrolyst of the present invention, is characterized in that described catalyst is by active part MnO 2and containing SiO 2tiO 2-SiO 2carrier part forms.
The present invention is to existing MnO 2the composition of catalyst resets, and adds TiO 2-SiO 2carrier part, wherein TiO 2with MnO 2there is strong interaction, optimize MnO 2catalytic performance (increase MnO 2selective to hydrolysis), and improve MnO 2recycle stability, and SiO 2can acidic site be provided, add and can further improve MnO 2catalytic activity, reduce MnO 2catalytic temperature.On the basis of above scheme, the present invention improves the catalytic performance of described hydrolyst further from following two aspects.
1. the acquisition of active part and carrier part.
(1) MnO 2acquisition:
As described in the background section, KMnO 4with MnSO 4redox reaction produce MnO 2produce the reaction of niacinamide as the hydrolysis of catalyst nicotinonitrile, end reaction productive rate can reach about 80%, in addition, also can make KMnO 4obtained MnO is reacted with organic matter 2, some experimental results show, KMnO 4the MnO obtained with inorganic salts generation redox reaction 2catalytic activity is KMnO comparatively 4the MnO obtained with organic matter generation redox reaction 2slightly high, therefore those skilled in the art may be more prone to adopt KMnO 4mnO is prepared with the redox reaction of inorganic salts 2, active part MnO of the present invention 2first reduce KMnO by organic matter 4obtain MnO 2, then to gained MnO 2acidifying is reduced, logical oxygen roasting forms, the redox reaction of the redox reaction also namely adopting first organic matter to participate in generally then inorganic salts participation again, and the mode of last oxidizing roasting is carried out, through X-diffraction and infrared spectrum analysis display, active part MnO of the present invention 2have and KMnO 4the MnO obtained with inorganic salts generation redox reaction 2(such as KMnO 4in neutral environment, obtained MnO is reacted with manganese chloride 2) different crystal structure, and at least at MnO 2specific area and specific volume have obvious advantage, thus make MnO 2catalytic activity has obvious lifting.
As a special case, active part MnO of the present invention 2be made up of following steps:
KMnO will be derived from 4the MnO generated is reacted with organic matter 2acidifying, then adjust ph is to 6.0-6.5, and form manganese intermediate compound, described organic matter comprises toluene, benzyl halide, nitrotoleune and C1-C3 alkyl pyridine;
Add carbonic hydroammonium to manganese intermediate compound, generate sediment, then oxygen, high-temperature roasting are led to sediment.Sintering temperature is arranged on 300-350 DEG C usually, to guarantee to obtain active part MnO 2.
(2) TiO 2acquisition:
There is TiO in occurring in nature 2three kinds of variants: Rutile Type (tetragonal crystal), plate titanium phase (orthorhombic crystal), sharp titanium phase (tetragonal crystal), wherein sharp titanium phase TiO 2the specific area that tool is high and stronger surface acidity, strong acid center is present in its surface and causes and MnO 2stronger interaction, importantly, the present invention finds MnO used in the present invention 2crystal structure and anatase TiO 2comparatively close to and there is brilliant structure and join suitable, MnO 2crystal is very easy to from TiO 2upper oriented epitaxial growth, thus expose Mn to greatest extent 4+(Mn 4+the electronics in hydrone on oxygen atom can be attracted, thus easily lose a proton, produce acid oh group), be conducive at MnO 2acid hydroxy group group needed for surface aggregation hydrolysis, makes MnO 2there is higher catalytic efficiency.
General, sharp titanium phase TiO 2industrial sulfate process preparation can be adopted, but the TiO that this legal system is standby 2the mass percent of middle sulfate ion can reach 1.7%-1.9%, and the impurity such as too much sulfate ion may make TiO 2-SiO 2carrier part is sharp titanium phase TiO in preparation process 2change to Rutile Type, cause the catalytic efficiency that hydrolyst is lower.
For this reason, the invention provides solution: too much sulphur roasting direct or by TiO 2first be immersed in then roasting removing in aqueous slkali.By this scheme, TiO 2-SiO 2in carrier part, the mass percent of sulphur is less than 0.5%.
2. the proportioning of active part and carrier part is arranged.
Usually, TiO in carrier part of the present invention 2with SiO 2mass ratio be (85-87): (15-13), and on this basis, by MnO 2mass percent in hydrolyst is set to 15-20%, this setting makes hydrolyst possess high catalytic performance to many hydrolysis, such as hydrolyst being applied to nicotinonitrile is hydrolyzed in the hydrolysis of niacinamide, the conversion ratio of nicotinonitrile is more than 99.8%, and the selective of niacinamide reaches more than 98.5%.
Second Problem to be solved by this invention is to provide a kind of preparation method of hydrolyst, and the method comprises:
A. by TiOSO 4with containing SiO 2ludox co-precipitation obtain TiO 2-SiO 2carrier part;
B. KMnO will be derived from 4the MnO generated is reacted with organic matter 2acidifying, then adjust ph is to 6.0-6.5, and form manganese intermediate compound, described organic matter comprises toluene, benzyl halide, nitrotoleune and C1-C3 alkyl pyridine;
C. add ammonium carbonate to manganese intermediate compound, the depositions settle of generation is in TiO 2-SiO 2carrier part, forms intermediate solid;
D. oxygen, high-temperature roasting are led to intermediate solid, after cooling, grind to form graininess hydrolyst.
Although select TiOSO in a step 4as reaction raw materials, there is the danger introducing sulfate ion to hydrolyst, but due in Step d high-temperature roasting, the TiO of hydrolyst can be made 2-SiO 2in carrier part, the mass percent of sulphur is less than 0.5%.In addition, the preparation method of described hydrolyst also attempts to improve TiO 2-SiO 2the specific area of carrier part, controls the temperature of the high-temperature roasting of Step d such as, at rational scope, 300-350 DEG C, can make TiO 2-SiO 2average specific surface area reach 195.05m 2g -1.
3rd problem to be solved by this invention is to provide a kind of hydrolyst for the preparation of niacinamide method (i), the method initial feed be nicotinonitrile (ii), comprising:
（ii） （i）
1. the aqueous solution of hydrolyst and nicotinonitrile are (ii) mixed to get reactant mixture;
2. under alkali condition, reactant mixture is heated, make reaction temperature remain on 95-100 DEG C, form crude product feed liquid;
3. crude product feed liquid is purified and obtain niacinamide (i).
Due to the good catalytic of hydrolyst of the present invention, use the hydrolyst of minute quantity that nicotinonitrile just can be made (ii) to be converted into niacinamide smoothly (i), such as usually can use nicotinonitrile (ii) mole less than 8% hydrolyst, and the hydrolyst life-span is long, can be recycled more than 10 times.
In order to ensure the conversion ratio of nicotinonitrile more than 99.8%, and the selective of niacinamide reaches more than 98.5%, with MnO in hydrolyst 2molal quantity represent the molal quantity of hydrolyst, the use amount of hydrolyst be preferably not less than nicotinonitrile (ii) mole 2.9%, in fact, hydrolyst use amount lower than nicotinonitrile (ii) mole 2.9% can cause lower nicotinonitrile conversion ratio and niacinamide selective, and higher than the hydrolyst use amount of nicotinonitrile (ii) mole 4.0%, although nicotinonitrile conversion ratio can remain on high level, the selective of niacinamide reduces.
Detailed description of the invention
MnO in the hydrolyst that each embodiment uses 2source, by one of the product MnO of 3-picoline and potassium permanganate generation redox reaction 2there is provided, specifically can obtain MnO by method below 2source:
Take 30.5g organic matter, be dissolved in 200ml pyridine (note solution I), get 42.5g potassium permanganate in 150ml deionized water, stir continuously in 50 DEG C, after dissolving completely, be cooled to room temperature (note solution II); Under room temperature condition, solution I is added solution II, after reaction a period of time, suction filtration must precipitate, required manganese dioxide can be obtained in 110-115 DEG C of dry 2-3h after spending deionized water, described organic matter comprises toluene, benzyl halide, nitrotoleune and C1-C3 alkyl pyridine, and the methyl in described benzyl halide on phenyl ring meets by the condition of potassium permanganate oxidation.
The hydrolyst used can be made up of following methods:
TiO 2-SiO 2the preparation of carrier part: by TiOSO 4soluble in water, 50-60 DEG C of stirring in water bath, adds containing 30% mass percent SiO after dissolving completely 2ludox, stir standing certain hour and obtain mixed solution, dripping mass percent is the ammonia spirit of 20%, endpoint pH controls at 10-11, the suspension generated is in 35-40 DEG C of standing 8-10h, filter, wash the solid dry 10h at 105-110 DEG C obtained, then at 550 DEG C of roasting 5h, obtain TiO 2-SiO 2carrier part, above-mentioned TiOSO 4and SiO 2use amount should meet and make final TiO 2with SiO 2mass ratio be (85-87): (13-15);
MnO 2process: 5g is derived from KMnO 4the MnO generated is reacted with 3-picoline 2, 8g oxalic acid, 10-15g water, add the acidifying of 10-12g 6mol/L sulfuric acid solution, pH to 6-6.5 adjusted by concentrated ammonia liquor, forms manganese intermediate compound;
MnO 2at SiO 2-TiO 2the deposition of carrier part: add NH to manganese intermediate compound 4hCO 3and SiO 2-TiO 2carrier part, the depositions settle of generation is in TiO 2-SiO 2carrier part, washes 3-5 time, in 50 DEG C of dry 0.5-1h, forms intermediate solid;
Roasting to intermediate solid: intermediate solid is led to oxygen in 300-350 DEG C of high temperature, roasting, grinding obtain the hydrolyst particle that particle diameter is 0.08-0.15mm.
Technical staff can carry out the expansion of equal proportion to the addition participating in the various materials reacted in said method or reduce according to the actual requirements.
Embodiment 1-4:
1) hydrolyst getting hydrolyst 28.5g(embodiment 1,2,3 and 4 adopts the method preparation preparing hydrolyst in detailed description of the invention part, wherein MnO in embodiment 1,2,3,4 2the mass percent accounting for intermediate solid controls respectively at 5%-10%, 10%-15%, 15%-20%, 20%-25%), in 200ml there-necked flask A, add 50ml distilled water, be placed in 75 DEG C of water-baths, agitation as appropriate obtains the stable hydrolyst aqueous solution, for subsequent use;
2) get 150ml nicotinonitrile in 500ml there-necked flask B, the above-mentioned obtained hydrolyst aqueous solution is proceeded to flask B, with appropriate distilled water washing flask A, and cleaning solution is proceeded to flask B, appropriateness stirs and evenly mixs, and obtains reactant mixture;
3) get 15ml ammoniacal liquor (mass percent concentration 20%), add step 2) in mixed liquor, heating water bath, timing when temperature rises to 85 DEG C, controls reaction temperature 95-100 DEG C, reaction time 3-5h, rear sampling detects 3-cyano content, determines the extent of reaction;
4) after reacting completely, feed liquid after filtration, decolouring, filtration treatment, gained filtrate adopts HPLC method to analyze content composition, the conversion ratio of nicotinonitrile and catalyst choice.
Concrete outcome is in table 1:
Table 1
MnO 2Mass percent Reaction temperature Reaction time 3-CNP conversion ratio NSA is selective
Embodiment 1 5%-10% 96℃ 4h 45%-52% 95.3%
Embodiment 2 10%-15% 96℃ 4h 80%-85% 97.6%
Embodiment 3 15%-20% 96℃ 4h 99.8%-100% ＞98.5%
Embodiment 4 20%-25% 96℃ 4h 91%-95% 97.8%
Determine that the hydrolysis of catalysis nicotinonitrile obtains the optimal conditions of niacinamide: with the MnO prepared 2mass percent is the hydrolyst MnO of 15%-20% 2/ SiO 2-TiO 2(wherein SiO 2-TiO 2middle SiO 2mass percent is 13%-15%, gained SiO 2-TiO 2average specific surface area is 195.05m 2g -1) catalyzing hydrolysis nicotinonitrile, the mol ratio of hydrolyst and nicotinonitrile is 0.032-0.038(such as 0.035), reaction temperature 96-100 DEG C, reaction time 4h, nicotinonitrile conversion ratio about 100% under this condition, selectively reaches more than 98.5%.
Embodiment 5-7:
Preparation MnO 2/ TiO 2and pure MnO 2, wherein MnO 2/ TiO 2only MnO is with the difference of hydrolyst preparation method 2/ TiO 2do not add Ludox, and pure MnO 2preparation method be detailed description of the invention part MnO 2the preparation method in source, MnO 2/ SiO 2-TiO 2preparation method (the wherein MnO identical with the preparation method of detailed description of the invention partial hydrolysis catalyst of (i.e. hydrolyst) 2the mass percent accounting for intermediate solid controls at 15%-20%), (wherein embodiment 5 is by MnO to carry out Activity Assessment according to the method for embodiment 1 to 4 2replace hydrolyst, and embodiment 6 is by MnO 2/ TiO 2replace hydrolyst), active power is followed successively by MnO 2/ SiO 2-TiO 2> MnO 2/ TiO 2> MnO 2.
Concrete outcome is in table 2:
Table 2
Catalyst classification Reaction temperature Reaction time 3-CNP conversion ratio NSA is selective
Embodiment 5 MnO 2 96℃ 4h 90.58 % 96.26%
Embodiment 6 MnO 2/TiO 2 96℃ 4h 96.47% 98.13%
Embodiment 7 MnO 2/TiO 2-SiO 2 96℃ 4h ＞99.80% ＞98.50%

Claims (9)

1. a hydrolyst, is characterized in that by active part MnO 2and containing SiO 2tiO 2-SiO 2carrier part forms, described MnO 2crystal structure and anatase TiO 2there is brilliant structure joins suitable, described active part MnO 2first reduce KMnO by organic matter 4obtain MnO 2, then to gained MnO 2acidifying is reduced, and 300 DEG C-350 DEG C logical oxygen roastings form.
2. a kind of hydrolyst according to claim 1, is characterized in that described organic matter comprises toluene, benzyl halide, nitrotoleune and C1-C3 alkyl pyridine.
3. a kind of hydrolyst according to claim 1, is characterized in that described MnO 2mass percent in hydrolyst is 15-20%.
4. a kind of hydrolyst according to claim 1, is characterized in that TiO 2for sharp titanium phase TiO 2.
5. a kind of hydrolyst according to claim 1, is characterized in that TiO in described carrier part 2with SiO 2mass ratio be (85-87): (13-15).
6. a preparation method for hydrolyst described in claim 1, comprising:
A. by TiOSO 4with containing SiO 2ludox co-precipitation obtain TiO 2-SiO 2carrier part;
B. KMnO will be derived from 4the MnO generated is reacted with organic matter 2acidifying, then adjust ph is to 6.0-6.5, and form manganese intermediate compound, described organic matter comprises toluene, benzyl halide, nitrotoleune and C1-C3 alkyl pyridine;
C. add carbonic hydroammonium to manganese intermediate compound, the depositions settle of generation is in TiO 2-SiO 2carrier part, forms intermediate solid;
D. oxygen, 300 DEG C of-350 DEG C of roastings are led to intermediate solid, after cooling, grind to form graininess hydrolyst.
7. the preparation method of hydrolyst according to claim 6, is characterized in that described in a step, co-precipitation comprises TiO 2-SiO 2the roasting of carrier part.
8. hydrolyst described in claim 1 is for the preparation of a niacinamide method (i), initial feed be nicotinonitrile (ii), comprising:
（ii） （i）
1. the aqueous solution of hydrolyst described in claim 1 and nicotinonitrile are (ii) mixed to get reactant mixture;
2. under alkali condition, reactant mixture is heated, make reaction temperature remain on 95-100 DEG C, form crude product feed liquid;
3. crude product feed liquid is purified and obtain niacinamide (i).
9. a kind of niacinamide according to claim 8 preparation method (i), is characterized in that 1. in step, with MnO in hydrolyst 2molal quantity represent the molal quantity of hydrolyst, hydrolyst and nicotinonitrile mol ratio is (ii) 0.029-0.040, and 2. the reaction time of step is 3-5h.
CN201310135495.4A 2013-04-18 2013-04-18 Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst Active CN103252233B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310135495.4A CN103252233B (en) 2013-04-18 2013-04-18 Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310135495.4A CN103252233B (en) 2013-04-18 2013-04-18 Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst

Publications (2)

Publication Number Publication Date
CN103252233A CN103252233A (en) 2013-08-21
CN103252233B true CN103252233B (en) 2015-03-18

Family

ID=48956644

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310135495.4A Active CN103252233B (en) 2013-04-18 2013-04-18 Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst

Country Status (1)

Country Link
CN (1) CN103252233B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592106A (en) * 2014-10-23 2015-05-06 华中药业股份有限公司 Improvement preparation method of nicotinamide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101987827A (en) * 2009-08-07 2011-03-23 中国石油化学工业开发股份有限公司 Preparing method of organic carboxylic acid amide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11319558A (en) * 1998-05-13 1999-11-24 Mitsubishi Gas Chem Co Inc Hydration catalyst for cyanhydrin
DE102008001319A1 (en) * 2008-04-22 2009-10-29 Evonik Röhm Gmbh Catalyst for the conversion of carbonitriles
TW201102365A (en) * 2009-07-03 2011-01-16 China Petrochemical Dev Corp Method for producing organic carboxylic acid amide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101987827A (en) * 2009-08-07 2011-03-23 中国石油化学工业开发股份有限公司 Preparing method of organic carboxylic acid amide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
3-甲基吡啶氨氧化制3-氰基吡啶催化剂研究;倪康婧;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20071215(第06期);正文第21页1.3.3.3 V2O5/TiO2催化剂的结构 *
V2O5/TiO2催化剂表面钒氧物种的分散状态和催化性能;许波连等;《中国科学》;20020630;第32卷(第3期);第235页前言 *

Also Published As

Publication number Publication date
CN103252233A (en) 2013-08-21

Similar Documents

Publication Publication Date Title
CN106006732A (en) Method for preparing ammonium polyvanadate from high concentration vanadium liquid
CN101580464B (en) Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct
CN112495401B (en) Mo-doped MoO3@ZnIn2S4Z-system photocatalyst and preparation method and application thereof
CN102616836B (en) Preparation method of trivalent titanium solution
CN102153350B (en) Method for preparing potassium niobate nano powder
CN103007921B (en) Method for synthesizing carbon-doped BiVO4 photocatalyst by using microwave hydrothermal method
CN102949991A (en) Method for preparing BiVO4 film with photocatalysis performance by using sol-gel method
CN107382844A (en) A kind of method that nicotinic acid is produced using niacinamide usp as raw material
CN106430300A (en) Alkali-neutralization seed crystal external addition method for producing titanium dioxide
CN102828037A (en) Method of preparing low-silicon low-phosphorus potassium metavanadate solution from vanadium slag
CN103240073A (en) Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof
CN102432066B (en) Method for preparing titanium tetrachloride hydrolyzed crystal seed
CN103482700A (en) Preparation method of basic zirconium carbonate
CN103904343A (en) Preparation method of electrolyte for all-vanadium redox flow battery
CN116154244A (en) All-vanadium redox flow battery electrolyte and preparation method thereof
CN109928375B (en) Method for preparing iron phosphate by using monocalcium phosphate
CN103252233B (en) Hydrolysis catalyst and preparation method thereof, and method for preparing nicotinamide by utilizing hydrolysis catalyst
CN102557133B (en) Method for preparing fishbone-shaped and firewood-shaped BiVO4 powder by microwave hydrothermal method
CN101525752B (en) Clean production method for high-purity cobaltosic oxide powder
CN109772378A (en) Method for preparing highly active Fe doping BiOX light fenton catalyst and products thereof and application
CN113387851A (en) Preparation method of 4, 4' -dichlorodiphenyl sulfone
CN116259811B (en) Method for preparing vanadium electrolyte from sodium vanadate solution
CN102367180B (en) Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source
CN100566826C (en) A kind of method of preparing photocatalytic material by titanic iron ore ore concentrate wet chemical method
CN102557091A (en) Method for subsequent treatment of aluminum sulfate generated in technical process of extracting alumina from fly ash

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190424

Address after: 332000 Jishan Industrial Park, Pengze County, Jiujiang City, Jiangxi Province

Patentee after: Jiangxi brothers Pharmaceutical Co., Ltd.

Address before: 314407 Caijiashiqiao No. 3, Zhouwangmiao Town, Haining City, Jiaxing City, Zhejiang Province

Patentee before: Brother Science and Technology Co., Ltd.

TR01 Transfer of patent right