CN104402774A - Method for preparing CLT acid through continuous catalytic hydrogenation reduction - Google Patents
Method for preparing CLT acid through continuous catalytic hydrogenation reduction Download PDFInfo
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- CN104402774A CN104402774A CN201410674974.8A CN201410674974A CN104402774A CN 104402774 A CN104402774 A CN 104402774A CN 201410674974 A CN201410674974 A CN 201410674974A CN 104402774 A CN104402774 A CN 104402774A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for preparing CLT acid through continuous catalytic hydrogenation reduction. The method is performed in a set of ejecting circuit continuous reactor, adopts the ejecting circuit continuous reactor to simplify the catalytic hydrogenation reduction process flow and improve the hydrogenation reduction efficiency. Meanwhile, the method can effectively reduce spillage and loss of a catalyst, caused by frequent filtering during intermittent catalytic hydrogenation reduction to realize internal recycling of the catalyst so as to prolong the service life of the catalyst. In addition, when the method is used for preparing CLT acid through continuous catalytic hydrogenation reduction, a reaction kettle is relatively small in size, good in reaction stability, relatively low in dechlorination products in a reaction product, high in selectivity, less in by-products and relatively low in content of residual main nitro compounds, and the nitro conversion rate can be higher than 99.80%.
Description
Technical field
The invention belongs to organic chemical synthesis field, be specifically related to the method that CLT acid is prepared in the reduction of a kind of continuous catalytic hydrogenation.
Background technology
CLT acid has another name called 2-amino-4-methyl-5-chloro Phenylsulfonic acid, it is a kind of important organic red pigment intermediate, mainly for the manufacture of pigment dyestuff bronze red C, the bright red LG of rubber and Lithol Red etc., it is widely used in the painted of preparation ink, paint and coating and plastics and rubber.The CLT acid synthetic method of adopting at present work is both at home and abroad toluene sulfonation method substantially, and namely toluene is through sulfonation, chlorination, nitrated, obtains CLT acid finished product after reduction, acid out, press filtration and drying.
For the reducing process of CLT acid, what generally adopt both at home and abroad at present is iron powder reducing technique, a large amount of iron powders can be consumed in iron powder reducing process, labour intensity is larger, not only having large quantity of exhaust gas in reaction is discharged in air, and a large amount of iron mud in production process, can be produced, there is problem of environmental pollution.Because CLT acid is a kind of important organic red pigment intermediate, in order to the Sustainable development of this product, how utilizing catalytic hydrogenating reduction to substitute iron powder reducing becomes the Main way researched and developed at present.
At present, the research report being prepared by catalytic hydrogenating reduction to CLT acid is more, mainly contain following several method: one, utilize Pd/C to make catalyzer, in high-pressure hydrogenation reactor, adopt intermittent reaction mode to carry out catalytic hydrogenating reduction prepare CLT acid, there are the following problems for the method: (1) reactor volume is comparatively large, causes facility investment higher.(2) reaction stability is poor, and product dechlorination is higher, and selectivity is low, causes by product more.(3) there is catalyst activity component loss loss large, catalyst life is short, thus causes catalyzer high expensive; Two, utilize Pt/C to make catalyzer, in high-pressure hydrogenation reactor, adopt intermittent reaction mode to carry out catalytic hydrogenating reduction prepare CLT acid, there are the following problems for the method: (1) reactor volume is comparatively large, causes facility investment higher.(2) although catalytic hydrogenating reduction effect when utilizing Pt/C to make catalyzer is fine, product dechlorination is lower, but because the market price in CLT acid only has 25000-28000 yuan/ton, and the price of Pt/C is higher, in intermittent reaction mode, catalyst activity component loss loss is large, causes catalyzer high expensive.Three, the load of granule type carbon or aluminium sesquioxide supporting Pt type catalyzer is utilized, in fixed-bed reactor, adopt continuously feeding, continuous discharge and pass into the mode of hydrogen continuously, carry out continuous catalytic hydrogenation reduction preparation CLT acid, there are the following problems for the method: (1) temperature of reaction and pressure higher, require also high to the material of equipment and voltage withstand class, thus cause facility investment higher.(2) purity requirement of fixed-bed reactor to raw material is higher, otherwise because material impurity can easily cause granule type poisoning of catalyst to lose efficacy too much, thus cause the risk in large production larger, wayward, in addition because the purity of CLT acid nitro material is not very high, be therefore not suitable for carrying out continuous catalytic hydrogenation reduction preparation CLT acid.
Summary of the invention
Problem to be solved by this invention is the method that CLT acid is prepared in a kind of continuous catalytic hydrogenation reduction proposed for the deficiencies in the prior art, the process employs injection loop to react, achieve the continuous production of CLT acid, reaction stability is good, product dechlorination is lower, selectivity is high, and by product is less.
The method of CLT acid is prepared in a kind of continuous catalytic hydrogenation reduction, the method is realized by a set of injection loop reactive system, and this injection loop reactive system comprises top and the reactor of injector, recycle pump, water cooler, strainer, gas-liquid separator and reduced liquid receiving tank are housed;
The step of the method is as follows:
(1) be equipped with in the reactor of injector at top, first the aqueous solution of CLT acid itrated compound (2-nitro-4-methyl-5-chlorobenzenesulfonic acid) is added, then supported nickel catalyst is added, whole reactive system nitrogen replacement air twice, after using hydrogen exchange nitrogen twice again, start injection loop flow reactor recycle pump and make Matter Transfer, temperature of charge in flow reactor is risen to 60-65 DEG C, pass into hydrogen continuously, keep the hydrogen pressure in reactive system to be that 1.5-2MPa reacts;
(2) after the Matter Transfer in reactor being reacted 2-3 hour, under keeping the condition of Matter Transfer, use volume pump again with stable flow to pump CLT acid itrated compound (2-nitro-4-methyl-5-chlorobenzenesulfonic acid) aqueous solution in injection loop flow reactor, Controlling System temperature of reaction is at 60-65 DEG C simultaneously; While pumping into the CLT acid itrated compound aqueous solution with volume pump in injection loop flow reactor, open the discharging Self controlling valve spraying pot strainer in loop continuous reaction system, CLT acid (2-amino-4-methyl-5-chloro Phenylsulfonic acid) aqueous solution completed by catalytic hydrogenating reduction enters in gas-liquid separator after pot strainer filters, and reduced liquid enters in reduced liquid storage tank after gas-liquid separation.
In the present invention, this catalytic hydrogenating reduction reactive system used comprises:
With the exterior line of injector entrance and the small transfer line being communicated with reactor top and injector entrance bottom reactor, the injector being arranged on reactor top, connection reactor;
Described exterior line is provided with for the recycle pump of convey materials and for the water cooler that cools material and the discharge port for deriving reduzate;
Described discharge port is connected with strainer, gas-liquid separator and reduced liquid receiving tank in turn, is provided with the discharge valve controlling discharge velocity between discharge port and strainer.
Wherein, the entrance of injector can be one or more.
The present invention sprays loop flow reactor by adopting, continuous hydrogenation reduction is carried out to CLT acid itrated compound, whole reaction process is carried out under steady state conditions, a reactor, CLT acid is obtained continuously from reaction system, reduce the volume of reactor, and reaction stability is good, product dechlorination is lower, selectivity is high, and by product is less.
This preparation method's chemical equation is expressed as follows:
As preferably, described supported nickel catalyst is carbon load nickel catalyzer or tripolite loading nickel catalyzator, nickel content >=40% (mass percent).As further preferred, in step (1), nickel content is between 40 ~ 50%.
As preferably, the mass concentration of the aqueous solution of described CLT acid itrated compound is 15 ~ 30%.Now, the transformation efficiency of whole reduction reaction is high.
As preferably, in step (1), the consumption of described supported nickel catalyst is 0.1% ~ 1% of the quality of the aqueous solution of described CLT acid itrated compound.
As preferably, in step (1), the ratio between the add-on of the aqueous solution of CLT acid itrated compound and the speed of Matter Transfer is 5 ~ 10g:1g/min.Adopt this cycle rate, the material in reaction system can be made fully to mix, improve mass-transfer efficiency.
As preferably, in step (2), the ratio of the speed of Matter Transfer, feed rate and discharge velocity is 15 ~ 25g/min:1g/min:1g/min.
As preferably, the volume of described reactor is 2 ~ 3L;
In step (1), the quality of the aqueous solution of described CLT acid itrated compound is 500 ~ 700g;
In step (2), the speed of Matter Transfer is 100 ~ 110g/min, and the speed of the CLT acid itrated compound aqueous solution pumped into is 4 ~ 6g/min, and the speed of the CLT acid aqueous solution of discharging is 4 ~ 6g/min.Now, whole injection loop flow reactor is stable, and product can keep higher purity in a long time.
Reduced liquid detects nitro transformation efficiency >=99.8% by chemical process, by its dechlorination product assay≤0.2% of liquid-phase chromatographic analysis, and residual main nitro compounds≤0.05%.
The present invention compared with prior art, there is following remarkable beneficial effect: the mode 1, utilizing the method continuous hydrogenation, continuously feeding, continuous discharge, carry out catalytic hydrogenating reduction when preparing CLT acid, required reactor small volume, reaction stability is good, and in reaction product, dechlorination product assay is lower, selectivity is high, by product is less, and the content of residual main nitro compounds is also lower, and nitro transformation efficiency is up to more than 99.80%; 2, catalyzer utilizes at injection loop flow reactor internal recycle, and can effectively reduce the loss loss causing catalyzer in Batch reaction processes owing to frequently filtering, the internal recycle realizing catalyzer utilizes, to improve catalyst life.
Accompanying drawing explanation
Fig. 1 is device and the process flow diagram of continuous catalytic hydrogenation of the present invention reduction preparation CLT acid.
Embodiment
As shown in the figure, comprise for the reaction unit of continuous catalytic hydrogenation reduction preparation CLT acid in the present invention:
With the exterior line of injector entrance and the small transfer line being communicated with reactor top and injector entrance bottom reactor, the injector being arranged on reactor top, connection reactor;
Described exterior line is provided with for the recycle pump of convey materials and for the water cooler that cools material and the discharge port for deriving reduzate;
Described discharge port is connected with strainer, gas-liquid separator and reduced liquid receiving tank in turn.
Following examples further illustrate of the present invention, but the present invention is not limited thereto.
Embodiment 1
In the reactor (2L) spraying loop reactor, first the mass concentration adding 650g is the aqueous solution of the CLT acid itrated compound of 15% (2-nitro-4-methyl-5-chlorobenzenesulfonic acid), then adds 3g carbon load nickel catalyzer (nickel content is 41%);
Whole reactive system nitrogen replacement air twice, after using hydrogen exchange nitrogen twice again, start and spray loop flow reactor recycle pump, the temperature of charge in flow reactor is risen to 60 DEG C, pass into hydrogen continuously, keep the hydrogen pressure in reactive system to be 2MPa; After Matter Transfer in reactor is reacted 2 hours, Matter Transfer speed is 100g/min, in injection loop flow reactor, pump into CLT acid itrated compound (2-nitro-4-methyl-5-chlorobenzenesulfonic acid) aqueous solution that mass concentration is 15% with stable flow 5g/min with volume pump again, Controlling System temperature of reaction is at 60-65 DEG C simultaneously; While pumping into the CLT acid itrated compound aqueous solution with volume pump in injection loop flow reactor, open the discharging Self controlling valve (discharge velocity is 5g/min) spraying pot strainer in loop continuous reaction system, CLT acid (2-amino-4-methyl-5-chloro Phenylsulfonic acid) aqueous solution completed by catalytic hydrogenating reduction enters in gas-liquid separator after pot strainer filters, and reduced liquid enters in reduced liquid receiving tank after gas-liquid separation.
Adopt the above-mentioned mode passing into hydrogen, continuously feeding and continuous discharge continuously, carry out catalytic hydrogenating reduction and prepare the CLT acid aqueous solution.
In experiment reaction process, timing is from the sampling of reaction solution receiving tank ingress, and carry out detection nitro transformation efficiency and liquid-phase chromatographic analysis, specific experiment data see the following form:
Embodiment 2
In the reactor (2L) spraying loop reactor, first the mass concentration adding 650g is the aqueous solution of the CLT acid itrated compound of 15% (2-nitro-4-methyl-5-chlorobenzenesulfonic acid), then adds 3g carbon load nickel catalyzer (nickel content is 41%);
Whole reactive system nitrogen replacement air twice, after using hydrogen exchange nitrogen twice again, start and spray loop flow reactor recycle pump, the temperature of charge in flow reactor is risen to 60 DEG C, pass into hydrogen continuously, keep the hydrogen pressure in reactive system to be 2MPa; After Matter Transfer in reactor is reacted 2 hours, Matter Transfer speed is 100g/min, in injection loop flow reactor, pump into CLT acid itrated compound (2-nitro-4-methyl-5-chlorobenzenesulfonic acid) aqueous solution that mass concentration is 15% with stable flow 8g/min with volume pump again, Controlling System temperature of reaction is at 60-65 DEG C simultaneously; While pumping into the CLT acid itrated compound aqueous solution with volume pump in injection loop flow reactor, open the discharging Self controlling valve (discharge velocity is 8g/min) spraying pot strainer in loop continuous reaction system, CLT acid (2-amino-4-methyl-5-chloro Phenylsulfonic acid) aqueous solution completed by catalytic hydrogenating reduction enters in gas-liquid separator after pot strainer filters, and reduced liquid enters in reduced liquid receiving tank after gas-liquid separation.
Adopt the above-mentioned mode passing into hydrogen, continuously feeding and continuous discharge continuously, carry out catalytic hydrogenating reduction and prepare the CLT acid aqueous solution.
In experiment reaction process, timing is from the sampling of reaction solution receiving tank ingress, and carry out detection nitro transformation efficiency and liquid-phase chromatographic analysis, specific experiment data see the following form:
This embodiment result shows, feeding rate and discharge velocity are selected excessive, and whole system running can be made unstable, and the quality product of reaction can reduce gradually.
Claims (8)
1. the method for CLT acid is prepared in continuous catalytic hydrogenation reduction, it is characterized in that, the method is realized by a set of injection loop reactive system, and this injection loop reactive system comprises top and the reactor of injector, recycle pump, water cooler, strainer, gas-liquid separator and reduced liquid receiving tank are housed;
The step of the method is as follows:
(1) be equipped with in the reactor of injector at top, first the aqueous solution of CLT acid itrated compound is added, then supported nickel catalyst is added, whole reactive system nitrogen replacement air twice, after using hydrogen exchange nitrogen twice again, start and spray loop flow reactor recycle pump and makes Matter Transfer, the temperature of charge in flow reactor is risen to 60-65 DEG C, pass into hydrogen continuously, keep the hydrogen pressure in reactive system to be that 1.5-2MPa reacts;
(2) by the Matter Transfer reaction in reactor after 2-3 hour, under keeping the condition of Matter Transfer, then with volume pump with stable flow to the pump CLT acid itrated compound aqueous solution in injection loop flow reactor, while Controlling System temperature of reaction at 60-65 DEG C; While pumping into the CLT acid itrated compound aqueous solution with volume pump in injection loop flow reactor, open the discharging Self controlling valve spraying pot strainer in loop continuous reaction system, the CLT acid aqueous solution completed by catalytic hydrogenating reduction enters in gas-liquid separator after pot strainer filters, and reduced liquid enters in reduced liquid storage tank after gas-liquid separation.
2. the method for CLT acid is prepared in continuous catalytic hydrogenation reduction according to claim 1, and it is characterized in that, in step (1), described supported nickel catalyst is carbon load nickel catalyzer or tripolite loading nickel catalyzator, nickel content >=40%.
3. the method for CLT acid is prepared in continuous catalytic hydrogenation reduction according to claim 2, and it is characterized in that, in step (1), nickel content is between 40 ~ 50%.
4. the method for CLT acid is prepared in continuous catalytic hydrogenation reduction according to claim 1, and it is characterized in that, the mass concentration of the aqueous solution of described CLT acid itrated compound is 15 ~ 30%.
5. the method for CLT acid is prepared in continuous catalytic hydrogenation reduction according to claim 4, and it is characterized in that, in step (1), the consumption of described supported nickel catalyst is 0.1 ~ 1% of the quality of the aqueous solution of described CLT acid itrated compound.
6. the method for CLT acid is prepared in the continuous catalytic hydrogenation reduction according to claim 1 or 4, and it is characterized in that, in step (1), the ratio between the add-on of the aqueous solution of CLT acid itrated compound and the speed of Matter Transfer is 5 ~ 10g:1g/min.
7. the method for CLT acid is prepared in continuous catalytic hydrogenation according to claim 6 reduction, it is characterized in that, in step (2), the ratio of the speed of Matter Transfer, feed rate and discharge velocity is 15 ~ 25g/min:1g/min:1g/min.
8. the method for CLT acid is prepared in continuous catalytic hydrogenation reduction according to claim 1, it is characterized in that,
The volume of described reactor is 2 ~ 3L;
In step (1), the quality of the aqueous solution of described CLT acid itrated compound is 500 ~ 700g;
In step (2), the speed of Matter Transfer is 100 ~ 110g/min, and the speed of the CLT acid itrated compound aqueous solution pumped into is 4 ~ 6g/min, and the speed of the CLT acid aqueous solution of discharging is 4 ~ 6g/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382793A (en) * | 2017-08-02 | 2017-11-24 | 江苏仁欣化工股份有限公司 | A kind of method that catalytic hydrogenation prepares CLT acid |
| CN109369469A (en) * | 2018-11-29 | 2019-02-22 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid chloride |
| CN109438295A (en) * | 2018-11-29 | 2019-03-08 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid sulfonated bodies |
| CN109593053A (en) * | 2018-11-29 | 2019-04-09 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid itrated compound |
| CN109627194A (en) * | 2018-12-28 | 2019-04-16 | 甘肃银光聚银化工有限公司 | A method of the synthesis chloro- toluenesulfonic acid of 2- amino -5- |
| CN110354790A (en) * | 2019-08-15 | 2019-10-22 | 山东方明药业集团股份有限公司 | A kind of the industrialized production equipment and production method of root bark of tree peony phenol sulfonic acid |
| CN113755308A (en) * | 2021-09-17 | 2021-12-07 | 倪浩辰 | Straw biogas feeding device and straw biogas system |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5144065A (en) * | 1990-08-08 | 1992-09-01 | Bayer Aktiengesellschaft | Process for the preparation of aminoarylsulphonic acids |
| CN1260346A (en) * | 1998-12-01 | 2000-07-19 | 拜尔公司 | Method for preparing amino-aryl sulfonic acid |
| CN1190411C (en) * | 1998-12-12 | 2005-02-23 | 巴斯福股份公司 | Method for producing amines |
| CN102408362A (en) * | 2011-12-26 | 2012-04-11 | 高邮市助剂厂 | Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
| WO2012123469A1 (en) * | 2011-03-16 | 2012-09-20 | Basf Se | Optimized metering of reactants for a process for preparing aromatic amines by hydrogenation of nitroaromatics |
| CN102702042A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN102964278A (en) * | 2012-11-27 | 2013-03-13 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| CN104098475A (en) * | 2014-07-28 | 2014-10-15 | 淮安嘉诚高新化工股份有限公司 | Device and method for producing diaminotoluene (TDA) by continuous liquid phase catalysis hydrogenation reduction of dinitrotoluene (DNT) |
-
2014
- 2014-11-21 CN CN201410674974.8A patent/CN104402774B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5144065A (en) * | 1990-08-08 | 1992-09-01 | Bayer Aktiengesellschaft | Process for the preparation of aminoarylsulphonic acids |
| CN1260346A (en) * | 1998-12-01 | 2000-07-19 | 拜尔公司 | Method for preparing amino-aryl sulfonic acid |
| CN1190411C (en) * | 1998-12-12 | 2005-02-23 | 巴斯福股份公司 | Method for producing amines |
| WO2012123469A1 (en) * | 2011-03-16 | 2012-09-20 | Basf Se | Optimized metering of reactants for a process for preparing aromatic amines by hydrogenation of nitroaromatics |
| CN102408362A (en) * | 2011-12-26 | 2012-04-11 | 高邮市助剂厂 | Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
| CN102702042A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN102964278A (en) * | 2012-11-27 | 2013-03-13 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| CN104098475A (en) * | 2014-07-28 | 2014-10-15 | 淮安嘉诚高新化工股份有限公司 | Device and method for producing diaminotoluene (TDA) by continuous liquid phase catalysis hydrogenation reduction of dinitrotoluene (DNT) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382793A (en) * | 2017-08-02 | 2017-11-24 | 江苏仁欣化工股份有限公司 | A kind of method that catalytic hydrogenation prepares CLT acid |
| CN109369469A (en) * | 2018-11-29 | 2019-02-22 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid chloride |
| CN109438295A (en) * | 2018-11-29 | 2019-03-08 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid sulfonated bodies |
| CN109593053A (en) * | 2018-11-29 | 2019-04-09 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid itrated compound |
| CN109438295B (en) * | 2018-11-29 | 2021-05-28 | 浙江秦燕科技股份有限公司 | Method for preparing CLT acid sulfonate by continuous reaction |
| CN109627194A (en) * | 2018-12-28 | 2019-04-16 | 甘肃银光聚银化工有限公司 | A method of the synthesis chloro- toluenesulfonic acid of 2- amino -5- |
| CN110354790A (en) * | 2019-08-15 | 2019-10-22 | 山东方明药业集团股份有限公司 | A kind of the industrialized production equipment and production method of root bark of tree peony phenol sulfonic acid |
| CN110354790B (en) * | 2019-08-15 | 2024-02-20 | 山东方明药业集团股份有限公司 | Industrial production method of paeonol sulfonic acid |
| CN113755308A (en) * | 2021-09-17 | 2021-12-07 | 倪浩辰 | Straw biogas feeding device and straw biogas system |
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Address after: Shangyu Weiyi Industrial Park 312369 Zhejiang city of Shaoxing province Shangyu city Hangzhou Bay No. 1 Applicant after: ZHEJIANG QINYAN TECHNOLOGY CO., LTD. Address before: Shangyu Weiyi Industrial Park 312369 Zhejiang city of Shaoxing province Shangyu city Hangzhou Bay No. 1 Applicant before: Zhejiang Qinyan Chemical Co., Ltd. |
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