Title of Invention	METHOD FOR PRODUCING HYDROXYLAMINE SULPHATE
Abstract	The invention relates to the chemical industry, namely to the method for production of hydroxylamine sulfate (HAS) used for caprolactam productions. The invention method consists of preparation of the reaction mixture, catalytic oxidation of ammonia under the pressure more than 0.3 MPa, concentration of NOx-gas at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from NOx-gas concentration, vapor condensate from concentration of HAS solution and HAS synthesis. In so doing the heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution. Nitric acid condensate is concentrated up to the mass share of nitric acid about 40%, which is got out as a final product and can be used in nitric fertilizes production, and HAS solution is concentrated up to the mass share of 40% at the expense of the heat of the distillate's vapor, being formed when nitric acid condensate is concentrated. Due to improving of the method the capital costs and power consumption for the product manufacturing are reduced and process control is simplified.

Title of Invention

METHOD FOR PRODUCING HYDROXYLAMINE SULPHATE

Abstract

The invention relates to the chemical industry, namely to the method for production of hydroxylamine sulfate (HAS) used for caprolactam productions. The invention method consists of preparation of the reaction mixture, catalytic oxidation of ammonia under the pressure more than 0.3 MPa, concentration of NOx-gas at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from NOx-gas concentration, vapor condensate from concentration of HAS solution and HAS synthesis. In so doing the heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution. Nitric acid condensate is concentrated up to the mass share of nitric acid about 40%, which is got out as a final product and can be used in nitric fertilizes production, and HAS solution is concentrated up to the mass share of 40% at the expense of the heat of the distillate's vapor, being formed when nitric acid condensate is concentrated. Due to improving of the method the capital costs and power consumption for the product manufacturing are reduced and process control is simplified.

Full Text	FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10 and rule 13) 1." METHOD FOR PRODUCING HYDROXYLAMINE SULPHATE" 2.(a) UKRAINIAN STATE SCIENTIFIC AND RESEARCH INSTITUTE OF NITRIC INDUSTRY AND ORGANIC SYNTHESIS PRODUCTS(UKRGIAP) (b) UKRAINE (C) ul. Gorobtsa, 2,Dnieprodzerzhynsk, 51909,UKRAINE The following specification particularly describes the invention and the manner in which it is to be performed. 1 The invention relates to the chemical to the chemical industry, namely to the method for production of hydroxylamine sulfate (HAS) used for caprolactam production. Production of concentrated nitric monoxide, used in HAS synthesis, by catalytic oxidizing of ammonia is inevitably accompanied with formation of diluted nitric acid (see the patent of USA 3110563 published on 12.11.1963) which recuperation brings about significant capital and operating costs. There are different method of these wastes recuperation used in HAS production. It is known the method for HAS production included preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidizing of ammonia, stabilization of the NOx-gas composition by hydrogenation on the silver-manganic catalyst, its two-stage condensation be steam concentration, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from the first stage of NOx-gas concentration, catalysate after hydrogenation of the second stage of NOx-gas concentration, catalytic hydrogenation of this condensate in presence of platinum catalyst and HAS synthesis (see application EPO 945401, IPC6 C01B21/14, published in 1999). In this manner full recuperation of diluted nitric acid wastes is reached. However, this method is characterized with difficulty in control and significant capital and operating costs specified with need of the stages for NOx-gas stabilization, compression and catalytic hydrogenation of nitric acid condensate. Also heat of NOx-gas lost irrevocably. The most close on technical essence and reached effect is the method for HAS production including preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidizing of ammonia, stabilization of the produced NOx-gas by hydrogenation on the silver-manganic 2- catalyst, its two-stage concentration by steam condensation [see the patent RF 2045471, IPC6 C01B21/14, published in 10/10/1995, bulletin 28-prior knowledge]. 70% of condensate, containing nitric acid with mass share up to 0,3% is separated on the first stage of condensation, nitric acid with mass share up to 5-6% is formed on the second stage. Condensate from the first stage is sent for diluting of sulfuric acid, condensate from the second stage after evaporating up to 40-45% is heated up to 300 °C and mixed with the main stream of NOx-gas, coming for stabilization, and steam is sent for preparation of mixture: ammonia, oxygen, steam. As in above mentioned case, recuperation of diluted nitric acid wastes brings about significant complication of the process, its reliability and essential capital costs. The goal of the present invention is in improvement of the method of HAS production by the process changing - eliminating of the stages of catalytic hydrogenation of nitric acid condensate, NOx-gas stabilization and compressing, - and the process parameters so that the capital and operational costs become lower, control and adjustment become more simple. The put problem is solved in that in the method of HAS production including preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidizing of ammonium, NOx-gas concentration at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, sulfuric acid mixture, water, condensate from NOx-gas concentration and YAS synthesis, according the invention the catalytic oxidizing of ammonia is executed under the pressure more than 0,3 MPa, heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution, in so doing nitric acid condensate is concentrated up to the mass share of nitric acid not less than 40%, and YAS solution is concentrated up to the mass share of 40% at the expense of the heat of the 3 distillate vapor condensation, formed when nitric acid condensate concentrated. The condensate with the mass share of nitric acid about 40% is got out as a final product and can be used in nitric fertilizes production. The Fig. 1 shows the drawing illustrating the applying method. The method is realized in following way. For production of 1 ton of hydroxylamine in hour the reaction mixture consisting of 817,5 kg/hour of ammonia, 2052,6 kg/hour of oxygen and 4021 kg/hour of steam is prepared in mixer 1 and sent to the Reactor 2, where on the platinum gauzes the steam and oxygen conversion of ammonia under the pressure more than 0,3 MPa, for example 0,3-0,35 MPa, is realized. The heat of ammonia oxidation reaction is used for steam production, cooling NOx-gas in the Waste heat boiler of the Reactor 2. The produced NOx-gas comes to the Heater 3 of the tower for nitric acid condensate distillation, where the steam is condensed with separation of nitric acid condensate (NAC) and NOx-gas concentrates. The heat of steam condensation is used for concentration of nitric acid condensate from the mass share of 7-8.5% to the mass share of 40%. The gaseous distillate forming there and containing nitric acid with the mass share up to 0,25% comes to the Heat Exchanger 7, where HAS solution with the mass share about 24% is sent as a cooling agent. HAS solution, heated at the expense of condensation the distillate's steam comes to the Separator 8, where water is evaporated from solution under reduced pressure and at the temperature 60-85 °C. The concentrated solution contains HAS with the mass share about 40%. NOx-gas after Heater 3 of the Distillation Tower 6 comes to the Heat Exchanger 4, where condensation of the residual steam with forming of nitric acid condensate with the mass share of 7-8.5% and cooling of the concentrated NOx-gas down to 40 °C take place; then NOx-gas is purified from nitric oxide (IV) in the Scrubber 5 and sent to the Stage 4 of HAS synthesis 11 in amount of 1092 kg/hour. The concentrated distillate with the mass share of nitric acid 0,25% and also a part of the second vapor condensate (SV) after the Separator 8 and Condenser of the second vapor 9 sent for diluting of the concentrated sulfuric acid to the Stage 10. The residual from the Distillation Tower 6 with the mass share of nitric acid about 40% in amount of 1138 kg/hour (455 kg/hour of nitric oxide monohydrate) is got out as a final product and can be used in nitric fertilizes production. The tail gases (TG) from the reactors of HAS synthesis is sent to the Recuperation Unit 12 for burning. In the Table 1 for comparison is shown the data, illustrating of the HAS synthesis plant operation under the applying method and prior knowledge. It can be seen from the Table, that the specific consumption of raw material for the product fabrication is higher than in prior knowledge. But herewith in addition the nitric acid with the mass share of 40%, which can be used for preparing of the mineral fertilizers and desired product - HAS with the mass share of 40% instead of 24,6% are produced without additional power consumption. 5 Table 1 NH3 O2 H2O NO from the Unit 5 NO to the Stage 11 H2forhydro-genationof O2 H2 in the Stage 11 ∑H2 nitric acidcondensate40% HNO3 HAS Unit kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour % Under the prior knowledge (Patent RF No 2045471) 680 1707 3345 1071 1092 17.5 128.1 145.6 - - 24.6 Under the claimed method 817.5 2052.6 4021 1092 1092 - 128.1 128.1 1138 455 40 WE CLAIM: 1. The method for HAS production including preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidation of ammonia, concentration of NOx-gas at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from NOx-gas concentration and HAS synthesis different with that the catalytic ammonia oxidation is executed under the pressure more than 0.3 MPa, heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution, in so doing nitric acid condensate is concentrated up to the mass share of nitric acid not less than 40% and HAS solution is concentrated up to the mass share of 40% at the expense of the heat of the distillate's vapor, being formed when nitric acid condensate is concentrated. 2. A method for producing hydroxylamine sulphate as claimed substantially as herein described with forgoing description and figures. Dated this 23rd day of February 2006. Dr. Rajeshkumar H. Acharya Advocate & Patent Agent For and on Behalf of Applicant 7 ABSTRACT The invention relates to the chemical industry, namely to the method for production of hydroxylamine sulfate (HAS) used for caprolactam production. The inventive method consists of preparation of the reaction mixture, catalytic oxidation of ammonia under the pressure more than 0.3 MPa, concentration of NOx-gas at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from NOx-gas concentration, vapor condensate from concentration of HAS solution and HAS synthesis. In so doing the heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution. Nitric acid condensate is concentrated up to the mass share of nitric acid about 40%, which is got out as a final product and can be used in nitric fertilizes production, and HAS solution is concentrated up to the mass share of 40% at the expense of the heat of the distillate's vapor, being formed when nitric acid condensate is concentrated. Due to improving of the method the capital costs and power consumption for the product manufacturing are reduced and process control is simplified.

Full Text

FORM 2
THE PATENT ACT 1970
(39 of 1970) &
The Patents Rules, 2003 COMPLETE SPECIFICATION
(See section 10 and rule 13)
1." METHOD FOR PRODUCING HYDROXYLAMINE SULPHATE"
2.(a) UKRAINIAN STATE SCIENTIFIC AND RESEARCH INSTITUTE OF NITRIC INDUSTRY AND ORGANIC SYNTHESIS PRODUCTS(UKRGIAP)
(b) UKRAINE (C) ul. Gorobtsa, 2,Dnieprodzerzhynsk, 51909,UKRAINE
The following specification particularly describes the invention and the manner in which it is to be performed.
1

The invention relates to the chemical to the chemical industry, namely to the method for production of hydroxylamine sulfate (HAS) used for caprolactam production.
Production of concentrated nitric monoxide, used in HAS synthesis, by catalytic oxidizing of ammonia is inevitably accompanied with formation of diluted nitric acid (see the patent of USA 3110563 published on 12.11.1963) which recuperation brings about significant capital and operating costs. There are different method of these wastes recuperation used in HAS production. It is known the method for HAS production included preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidizing of ammonia, stabilization of the NOx-gas composition by hydrogenation on the silver-manganic catalyst, its two-stage condensation be steam concentration, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from the first stage of NOx-gas concentration, catalysate after hydrogenation of the second stage of NOx-gas concentration, catalytic hydrogenation of this condensate in presence of platinum catalyst and HAS synthesis (see application EPO 945401, IPC6 C01B21/14, published in 1999).
In this manner full recuperation of diluted nitric acid wastes is reached. However, this method is characterized with difficulty in control and significant capital and operating costs specified with need of the stages for NOx-gas stabilization, compression and catalytic hydrogenation of nitric acid condensate. Also heat of NOx-gas lost irrevocably.
The most close on technical essence and reached effect is the method for HAS production including preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidizing of ammonia, stabilization of the produced NOx-gas by hydrogenation on the silver-manganic
2-

catalyst, its two-stage concentration by steam condensation [see the patent RF 2045471, IPC6 C01B21/14, published in 10/10/1995, bulletin 28-prior knowledge]. 70% of condensate, containing nitric acid with mass share up to 0,3% is separated on the first stage of condensation, nitric acid with mass share up to 5-6% is formed on the second stage. Condensate from the first stage is sent for diluting of sulfuric acid, condensate from the second stage after evaporating up to 40-45% is heated up to 300 °C and mixed with the main stream of NOx-gas, coming for stabilization, and steam is sent for preparation of mixture: ammonia, oxygen, steam. As in above mentioned case, recuperation of diluted nitric acid wastes brings about significant complication of the process, its reliability and essential capital costs.
The goal of the present invention is in improvement of the method of HAS production by the process changing - eliminating of the stages of catalytic hydrogenation of nitric acid condensate, NOx-gas stabilization and compressing, - and the process parameters so that the capital and operational costs become lower, control and adjustment become more simple.
The put problem is solved in that in the method of HAS production including preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidizing of ammonium, NOx-gas concentration at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, sulfuric acid mixture, water, condensate from NOx-gas concentration and YAS synthesis, according the invention the catalytic oxidizing of ammonia is executed under the pressure more than 0,3 MPa, heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution, in so doing nitric acid condensate is concentrated up to the mass share of nitric acid not less than 40%, and YAS solution is concentrated up to the mass share of 40% at the expense of the heat of the
3

distillate vapor condensation, formed when nitric acid condensate concentrated. The condensate with the mass share of nitric acid about 40% is got out as a final product and can be used in nitric fertilizes production.
The Fig. 1 shows the drawing illustrating the applying method.
The method is realized in following way.
For production of 1 ton of hydroxylamine in hour the reaction mixture consisting of 817,5 kg/hour of ammonia, 2052,6 kg/hour of oxygen and 4021 kg/hour of steam is prepared in mixer 1 and sent to the Reactor 2, where on the platinum gauzes the steam and oxygen conversion of ammonia under the pressure more than 0,3 MPa, for example 0,3-0,35 MPa, is realized. The heat of ammonia oxidation reaction is used for steam production, cooling NOx-gas in the Waste heat boiler of the Reactor 2. The produced NOx-gas comes to the Heater 3 of the tower for nitric acid condensate distillation, where the steam is condensed with separation of nitric acid condensate (NAC) and NOx-gas concentrates. The heat of steam condensation is used for concentration of nitric acid condensate from the mass share of 7-8.5% to the mass share of 40%. The gaseous distillate forming there and containing nitric acid with the mass share up to 0,25% comes to the Heat Exchanger 7, where HAS solution with the mass share about 24% is sent as a cooling agent. HAS solution, heated at the expense of condensation the distillate's steam comes to the Separator 8, where water is evaporated from solution under reduced pressure and at the temperature 60-85 °C. The concentrated solution contains HAS with the mass share about 40%. NOx-gas after Heater 3 of the Distillation Tower 6 comes to the Heat Exchanger 4, where condensation of the residual steam with forming of nitric acid condensate with the mass share of 7-8.5% and cooling of the concentrated NOx-gas down to 40 °C take place; then NOx-gas is purified from nitric oxide (IV) in the Scrubber 5 and sent to the Stage
4
of HAS synthesis 11 in amount of 1092 kg/hour. The concentrated distillate with the mass share of nitric acid 0,25% and also a part of the second vapor condensate (SV) after the Separator 8 and Condenser of the second vapor 9 sent for diluting of the concentrated sulfuric acid to the Stage 10. The residual from the Distillation Tower 6 with the mass share of nitric acid about 40% in amount of 1138 kg/hour (455 kg/hour of nitric oxide monohydrate) is got out as a final product and can be used in nitric fertilizes production. The tail gases (TG) from the reactors of HAS synthesis is sent to the Recuperation Unit 12 for burning.
In the Table 1 for comparison is shown the data, illustrating of the HAS synthesis plant operation under the applying method and prior knowledge.
It can be seen from the Table, that the specific consumption of raw material for the product fabrication is higher than in prior knowledge. But herewith in addition the nitric acid with the mass share of 40%, which can be used for preparing of the mineral fertilizers and desired product - HAS with the mass share of 40% instead of 24,6% are produced without additional power consumption.
5
Table 1
NH3 O2 H2O NO from the Unit 5 NO to the Stage 11 H2forhydro-genationof O2 H2 in the Stage 11 ∑H2 nitric acidcondensate40% HNO3 HAS
Unit kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour kg/hour %
Under the prior knowledge (Patent RF No 2045471) 680 1707 3345 1071 1092 17.5 128.1 145.6 - - 24.6
Under the claimed method 817.5 2052.6 4021 1092 1092 - 128.1 128.1 1138 455 40

WE CLAIM:
1. The method for HAS production including preparation of the reaction mixture of ammonia, oxygen and steam, catalytic oxidation of ammonia, concentration of NOx-gas at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from NOx-gas concentration and HAS synthesis different with that the catalytic ammonia oxidation is executed under the pressure more than 0.3 MPa, heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution, in so doing nitric acid condensate is concentrated up to the mass share of nitric acid not less than 40% and HAS solution is concentrated up to the mass share of 40% at the expense of the heat of the distillate's vapor, being formed when nitric acid condensate is concentrated.
2. A method for producing hydroxylamine sulphate as claimed substantially as herein described with forgoing description and figures.
Dated this 23rd day of February 2006.

Dr. Rajeshkumar H. Acharya
Advocate & Patent Agent
For and on Behalf of Applicant

7

ABSTRACT
The invention relates to the chemical industry, namely to the method for production of hydroxylamine sulfate (HAS) used for caprolactam production. The inventive method consists of preparation of the reaction mixture, catalytic oxidation of ammonia under the pressure more than 0.3 MPa, concentration of NOx-gas at the expense of steam condensation, mixing of the concentrated NOx-gas with hydrogen, mixture of sulfuric acid, water, condensate from NOx-gas concentration, vapor condensate from concentration of HAS solution and HAS synthesis. In so doing the heat of NOx-gas is used for concentration of nitric acid condensate and HAS solution. Nitric acid condensate is concentrated up to the mass share of nitric acid about 40%, which is got out as a final product and can be used in nitric fertilizes production, and HAS solution is concentrated up to the mass share of 40% at the expense of the heat of the distillate's vapor, being formed when nitric acid condensate is concentrated. Due to improving of the method the capital costs and power consumption for the product manufacturing are reduced and process control is simplified.

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Patent Number

219432

Indian Patent Application Number

222/MUMNP/2006

PG Journal Number

33/2008

Publication Date

15-Aug-2008

Grant Date

06-May-2008

Date of Filing

24-Feb-2006

Name of Patentee

UKRAINIAN STATE SCIENTIFIC AND RESEARCH INSTITUTE OF NITRIC INDUSTRY AND ORGANIC SYNTHESIS PRODUCTS (UKRGIAP)

Applicant Address

Inventors:

#	Inventor's Name	Inventor's Address
1	BARABASH, Ivan Ivanovich
2	KONOPLINA, Olga Viktorovna
3	MAMEDOV ABIL ABASOVICH

PCT International Classification Number

C01B21/14

PCT International Application Number

PCT/UA2004/000031

PCT International Filing date

2004-05-18

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2003087438	2003-08-06	Ukraine