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GB1584702A – Process for the preparation of sodium bisulphate
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GB1584702A – Process for the preparation of sodium bisulphate
– Google Patents
Process for the preparation of sodium bisulphate

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Publication number
GB1584702A

GB1584702A
GB18660/77A
GB1866077A
GB1584702A
GB 1584702 A
GB1584702 A
GB 1584702A
GB 18660/77 A
GB18660/77 A
GB 18660/77A
GB 1866077 A
GB1866077 A
GB 1866077A
GB 1584702 A
GB1584702 A
GB 1584702A
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United Kingdom
Prior art keywords
melt
sodium
sodium bisulphate
sulphate
temperature
Prior art date
1976-05-05
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.)

Expired

Application number
GB18660/77A
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Hoechst AG

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Hoechst AG
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1976-05-05
Filing date
1977-05-04
Publication date
1981-02-18

1977-05-04
Application filed by Hoechst AG
filed
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Hoechst AG

1981-02-18
Publication of GB1584702A
publication
Critical
patent/GB1584702A/en

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legal-status
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Classifications

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM

C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general

C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates

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

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P20/00—Technologies relating to chemical industry

Y02P20/10—Process efficiency

Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Description

(54) PROCESS FOR THE PREPARATION OF SODIUM
BISULPHATE
(71) We, HOECHST AKTIENGES
ELLSCHAFT, a body corporate organised according to the laws of the Federal
Republic of Germany, of 6230 Frankfurt/
Main 80, Postfach 80 03 20, Federal
Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to the preparation of sodium bisulphate from sodium chloride or sodium sulphate, and sulphuric acid.
Sodium bisulphate may be prepared continuously by introducing sodium chloride or sodium sulphate and concentrated sulphuric acid into a sodium bisulphate melt in a cast iron retort with exterior heating (cf. Ullmann, Enzyklopädie der technischen Chemie, 3rd edition, volume 15, page 72). A part of the melt is drawn off continuously and transformed into the commercial form of sodium bisulphate by granulation.
This use of cast iron retorts with indirect heating for the preparation of sodium bisulphate involves substantial disadvantages.
The retorts are corroded by the melt and, consequently, their service life is limited to about 1000 to 2000 hours, and replacing them by new retorts iis rather expensive.
Moreover the capacity of the retorts is very limited, as the heat must be transferred through the bottom of the retort. Finally, indirect heating is not very efficient from the thermoeconomical point of view.
The heat energy required for the endothermic preparation of sodium bisulphate from the above raw material can be transferred to the reactor by other methods. For the concentration of salt solutions and sulphuric
acids of low strength direct heating of the evaporators by means of oil- or gas-heated
immersion heaters has proved advantageous, and immersion heaters have been used in industry for the generation of heat in the preparation of sodium bisulphate. In this method lined retorts are used to prevent the corrosion of the cast iron retorts which occurs with this form of heating. Lined retorts have a service life of several years and are far more thermoeconomical.
In a process commonly used in industry the source of heat (immersion heater) is separated from the actual reaction zone so that the combustion gases from the immersion heater do not dilute the hydrogen chloride evolved. The melt is passed first through a combustion chamber equipped with an immersion heater, where it is heated, and then to a separator where it is freed from the combustion gases. Finally, the melt is recycled to the reactor, where further quantities of sodium bisulphate are formed, fresh hydrogen chloride is evolved, and sodium salt and sulphuric acid are added.
One disadvantage of the above method is, however, that frequently a considerable amount of sodium bisulphate, up to 25%, is discharged from the separator with the combustion gases in the form of very fine drops.
This loss may be avoided by technical measures, for example by the use of rather long cooling towers, centrifugal separators or electrofilters; these measures are, however, very complicated, owing to the fact that either the retained bisulphate must be recycled through heated conduits or it solidifies.
We have now found that the quantity of discharged sodium bisulphate can be reduced when the composition of the melt differs slightly. from the stoichiometric composition of sodium bisulphate (Na+ :HSO4-=l:l).
The invention provides a process for the preparation of sodium bisulphate which comprises reacting sodium chloride and/or sodium sulphate with sulphuric acid in a reactor charged with molten sodium bisulphate, the reactor being heated by an immersion heater, whereby combustion gases are formed, and the molar ratio of Na: S in the melt being in the range of from 1.01:1 to 1.07:1, preferably 1.02:1 to 1.06:1.
“Na” represents the number of moles of sodium ions in the melt and “S” represents the number of moles of sulphur in the form of oxyanions of sulphur (e.g. HSO4-+SO42+).
Preferably the reaction is a continuous process carried out in a submerged combustion burner, a circulation reactor which circulates the melt, and preferably reaction gas (e.g.
HC1) and combustion gases from the im mersion heater are drawn off at different points. A mixture of sodium chlorine and sodium sulphate can be used.
The molar ratio Na+:SO4– of from 1.07 to 1.01 corresponds to a melt containing from 93 to 99 /O of NaHSO4, the remainder being Na2SO4. If the composition of the melt changes, the amount of freed sodium salt (NaCI and/or Na2SO4) or sulphuric acid may be added or altered. The feed sodium salt reacts very rapidly with sulphuric acid, and therefore the composition of the melt may generally be determined by analysing a sample thereof. The composition of the melt can be determined more easily, however, by a conductivity measurement as follows. In order to remove a small quantity of hydrogen chloride from the combustion gases, a washing vessel is mounted after the separator, which is suitably operated with repumped water.
Under constant washing conditions (constant water current) there is a relation between the composition of the melt and the discharge in the gas phase and between this discharge and the electrical conductivity of the water which leaves the washing vessel: the conductivity of the wash water is increased with an increasing discharge. Because the quantity discharged depends on the composition of the melt, there is a relation, which is not necessarily linear but which can be represented by a calibration curve, between the conductivity of the wash water and the composition of the melt. The conductivity of the water (caused by the melt discharging NaHSO4) is high at a molar ratio of Na:S of 1.07:1 and low at a ratio of 1.101:1. For molar ratios smaller than 1.01:1, the conductivity and the discharge are low and generally constant.
However, in these cases, the product obtained can be granulated only with difficulty, as it has a tendency to become sticky.
This relation between the composition of the melt, the discharge and the conductivity of the wash water makes it possible to control the composition of the melt by measuring the conductivity of the waste water and an analysis of the melt is not required. Thus the reactor may be operated economically. This surprising behaviour is probably due to a considerable variation of the viscosity or of the surface tension of the melt with composition.
For most purposes a small content of sodium sulphate in technical grade sodium bisulphate is not important. The process of the invention uses molten sodium bisulphate as a solvent. Reaction temperatures of from 190 to 400 C, especially from 200 to 300 preferably of from 240 to 280″C, are advantageous.
The invention will now be illustrated by way of example only, by reference the accompanying drawing which shows a sectional view of an apparatus suitable for carrying out the process of the invention.
In use, sodium chloride or sodium sulphate and sulphuric acid are fed to a reactor (1) by an opening (2). The reaction gas leaves the reactor at an opening (3); when sodium chloride has been used the reaction gas consists of hydrogen chloride which may be used for the preparation of hydrochloric acid. A stirrer (10) serves to mix the introduced sodium salt rapidly with the liquid phase (6) consisting of molten sodium bisulphate. When aqueous solutions of sodium salts or diluted sulphuric acids or waste sulphuric acids are used, they are suitably introduced into an immersion heater zone (4) or into a separation zone (18). (This method is not shown lin the drawing). A portion of the liquid phase (6) is drawn off continuously from the reactor (1) through an opening (7). If desired, this portion may be granulated, for example in a spray tower (not shown).A further portion of the melt leaves the reactor at an opening (8) and is recycled to the immersion heater zone (4), where it is heated by an immersion heater (9) and then recycled to the reactor (1). A baffle plate (5) prevents the simultaneous transition of the combustion gases of the immersion heater into the reactor.
The combustion gases leave the separation zone (18) via a conduit (11) and enter into a washing vessel (12) whereby they are sprayed by a nozzle (14) with fresh water, which enters via a conduit (13). The conductivity of the water leaving via a conduit (15) is measured continuously in a cell (16). The purified combustion gases are discharged in the open air through a conduit (17).
The product obtained by the process of the invention can be granulated in known manner.
It may for example be transformed into scales or it may be sprayed in a cooling tower or on to a cooling strip. It has been ascertained, however, that the granulated sodium bisulphate produced from a melt is mainly present in a vitreous, metastable state, and therefore it can be processed only with difficulty. When this granulated product is stored in silos, barrels or sacks, its metastable phase is transformed into the stable phase over approximately 24 hours, and a considerable quantity of heat is evolved whereby the temperature may increase by up to 100″C. At the same time the product hardens to such a degree that it can be transformed into a form ready for use only with considerable expenditure, by crushing and sieving it. Freshly granulated product in the metastable state can also only be crushed with difficulty, as it behaves like a tough mass.Prior to storage or further processing it is therefore necessary to transform the granules largely or entirely into a stable form.
The acceleration of the transformation of the metastable form of granulated sodium bisulphate into the stable form may be carried out by the process of our copending application No. 7938193 (Serial No. 1584193).
According to this process sodium bisulphate granules are prepared by granulating molten sodium bisulphate and subsequently keeping the granulated final product for at least one minute at a temperature in the range of from 60 to 140″C. The resulting product consists of non-sticking granules. The melt may be granulated in any suitable manner, for example by spraying in a spray tower (whereby the liquid bisulphate solidifies during the free fall), by solidification on a cooling strip or on a scale roll.
The transformation into the stable phase in the given temperature range takes place faster the higher the temperature. At a temperature of from 50 to 60″C the transformation requires about 24 hours, at a temperature of 100″C about 10 minutes and at a temperature of from 120 to 140″C about 1 minute. The transformation could therefore be carried out at a temperature in the range of from 50 to 60 , but long residence times are not very economical. A temperature in the range of from 120 to 140″C is preferred.
A product which has not been stabilized may be subject to a sudden temperature increase accompanied by agglomeration, even after several days, whereas the stabilized granulate is storable without difficulty over a long period of time.
A further process for preparing sodium bisulphate granules is described and claimed in our copending application No. 7 943 993 (Serial No. 1 584 704). In this process the molten sodium bicarbonate is granulated in the presence of divided calcium sulphate, magnesium sulphate, barium sulphate, sodium sulphate or sodium bisulphate or a mixture of two or more such compounds in an amount of from 0.1 to 5% by weight, the compound or compounds being present before granulation.
The transformation of the metastable granulated sodium bisulphate is accelerated by these additives, and again non-sticking granules are produced. The compound or compounds may be added to the melt after it has been prepared and before granulation. However, instead of adding pure magnesium or calcium sulphate, crude non-purified rock salt, which contains these sulphates, may be used as a starting material in the preparation of the bisulphate. A portion of at least 20% by weight of non-purified rock salt is advantageous. The addition of finely pulverized sodium bisulphate or sodium sulphate is only advisable when it is effected shortly before the granulation. Silicates have proved inefficient.
The transformation of the metastable sodium bisulphate into the stable form can also be accelerated by increasing the water content of the melt to 0.01 to 3% by weight of water, prior to granulation. Non-sticking granules are produced.
This variant of the process according to the invention is applicable, for example, to granulation on a scale roll, and, preferably, to spraying in a cooling tower, whereby the molten sodium bisulphate solidifies during the free fall. It is thought that in the presence of water, primary salt hydrates are formed which act as catalyst for the transformation of the metastable phase into the stable phase.
For transforming the metastable form of sodium sulphate into the stable form, it has moreover proved advantageous to adjust the temperature of the melt prior to granulating to be within a well defined range, from 186 to 236″C. The granules produced therefrom are non-sticking. The cooling speed in “C per unit of time is lower in this temperature range than when cooling a melt which has a temperature of from 240 to 280″C to the same final temperature and, as a consequence thereof, most of the sodium bisulphate solidifies in the desired stable phase. This applies especially to granulation in a spraying tower.
It is possible to use two or more of the processes described above for forming the stable form of sodium bisulphate. The effects of the individual measures are thereby increased.
The following Examples illustrate the invention:
EXAMPLE 1.
1820 kg of 95 /O technical grade sulphuric acid and 1140 kg of marine salt were fed per hour into a lined circulation reactor (diameter of the reactor about 3 m, total effective volume about 20 m3). The temperature of the sodium bisulphate melt was maintained at 255″C by burning 220 m3 per hour of hydrogen with air in an immersion heater. The sodium bisulphate content of the melt was 92.6% by weight, the remainder being sodium sulphate. 498 kg/hour of sodium bisulphate were discharged with the wash water of the washing vessel for the combustion gases. Due to this loss, the yield of sodium bisulphate withdrawn from the circulation reactor was only 78% of the theoretical yield.
In order to reduce the discharge of sodium bisulphate, the composition of the melt was adjusted to a content of 96.4% by weight of sodium bisulphate. This was achieved by adding marine salt at a rate of 990 kg/hour and sulphuric acid at a rate of 1675 kg/hour.
The losses of sodium bisulphate in the waste water were only of the order of 36 kg/hour.
EXAMPLE 2.
1950 1 of technical grade sulphuric acid (d= 1.84) and 2129 kg of marine salt were fed per hour into the circulation reactor.
The temperature of the melt was 260″C when 330 m3/hour of hydrogen were burnt with air. The melt was sprayed in a cooling tower through nozzles and the solidified granules were cooled to 35″C by means of cold air and then stored in containers. Over several hours, the product was subject to a self-heating to about 125″C, whereby the product agglomerated forming blocks as hard as stone.
Consequently, the product was not very suitable for further use.
EXAMPLE 3.
The reaction and granulation procedure were the same as in Example 2, except that the temperature of the solidified granules was adjusted to about 65″C by reducing the quantity of cooling air during spraying and by preheating the air. Moreover, the product was stored at this temperature for about 40 minutes. The solidified granules remained free flowing even after several weeks and could readily be further processed.
EXAMPLE 4.
The reaction and granulation operation were the same as that of Example 2, except that the solidified granules were cooled only to a temperature of about 100″C during granulation.
The temperature of 100″C was maintained for 10 minutes. This residence time was sufficient for the complete transformation of the metastable sodium bisulphate. Even after a rather long period of time the product did not agglomerate.
EXAMPLE 5.
The operation was as in Example 2, except that 100 kg/hour of finely divided calcium sulphate were added to the melt flowing from the reactor. After spraying in the cooling tower and cooling to 35 C the granulated product was substantially stable and could be stored without self-heating and agglomeration.
EXAMPLE 6.
Example 5 was repeated, except that the same quantity of magnesium sulphate was used instead of calcium sulphate. The granulated sodium bisulphate was completely stable.
EXAMPLE 7.
Example 5 was repeated, except that no calcium sulphate was added and that 22% by weight of the quantity of marine salt was replaced by non-purified industrial rock salt.
The result was the same as in Example 5.
EXAMPLE 8.
4000 kg per hour of sodium sulphate melt
(content of sodium bisulphate 96.5%) were
produced in the circulation reactor. The melt
was sprayed in the cooling tower (quantity of
steam 20 kg per hour) by means of bi
component nozzles. The product obtained was
substantialy stable and could be further pro
cessed without difficulty (water content: 0.15%).
EXAMPLE 9.
1100 1 of technical grade sulphuric acid
(d=1.84) and 1200 kg of marine salt were
fed into the circulation reactor per hour. The
temperature of the melt was 260 when 210
m3/hour of hydrogen were burnt with the air.
On its way to the spraying tower the melt was cooled to 220″C by a cooled tube mounted directly before the spraying nozzles. The
granules were cooled to 40″C by cooling air
in the spraying tower. The product only had
a moderate tendency to get sticky and could be further processed without essential difficulties.
WHAT WE CLAIM IS: 1. A process for the preparation of sodium bisulphate which comprises reacting sodium chloride and/or sodium sulphate with sulphuric acid in a reactor charged with molten sodium bisulphate, the reactor being heated by an immersion heater whereby combustion gases are formed, and the molar ratio of Na: S (as hereinbefore defined) in the melt being in the range of from 1.01:1 to 1.07:1.
2. A process as claimed in claim 1, wherein the molar ratio of Na: S is in the range of from 1.02:1 to 1.06:1.
3. A process as claimed in either claim 1 or claim 2, wherein the reaction is carried out in a circulation reactor which recycles the melt.
4. A process as claimed in claim 3, wherein the combustion gases from the immersion heater and the reaction gases are drawn off from the reactor at different points.
5. A process as claimed in any one of claims 1 to 4, wherein the combustion gases from the immersion heater are washed and the conductivity of the washing water is subsequently determined.
6. Aprocess as claimed in any one of claims 1 to 5, wherein the molten sodium bisulphate is withdrawn and subsequently granulated.
7. A process as claimed in claim 1, carried out substantially as described herein with reference to, and as illustrated by, the accompanying drawing.
8. A process as claimed in any one of claims 1 to 7, wherein the molten sodium bisulphate is granulated and subsequently held for at
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (17)

**WARNING** start of CLMS field may overlap end of DESC **.
EXAMPLE 2.
1950 1 of technical grade sulphuric acid (d= 1.84) and 2129 kg of marine salt were fed per hour into the circulation reactor.
The temperature of the melt was 260″C when 330 m3/hour of hydrogen were burnt with air. The melt was sprayed in a cooling tower through nozzles and the solidified granules were cooled to 35″C by means of cold air and then stored in containers. Over several hours, the product was subject to a self-heating to about 125″C, whereby the product agglomerated forming blocks as hard as stone.
Consequently, the product was not very suitable for further use.
EXAMPLE 3.
The reaction and granulation procedure were the same as in Example 2, except that the temperature of the solidified granules was adjusted to about 65″C by reducing the quantity of cooling air during spraying and by preheating the air. Moreover, the product was stored at this temperature for about 40 minutes. The solidified granules remained free flowing even after several weeks and could readily be further processed.
EXAMPLE 4.
The reaction and granulation operation were the same as that of Example 2, except that the solidified granules were cooled only to a temperature of about 100″C during granulation.
The temperature of 100″C was maintained for 10 minutes. This residence time was sufficient for the complete transformation of the metastable sodium bisulphate. Even after a rather long period of time the product did not agglomerate.
EXAMPLE 5.
The operation was as in Example 2, except that 100 kg/hour of finely divided calcium sulphate were added to the melt flowing from the reactor. After spraying in the cooling tower and cooling to 35 C the granulated product was substantially stable and could be stored without self-heating and agglomeration.
EXAMPLE 6.
Example 5 was repeated, except that the same quantity of magnesium sulphate was used instead of calcium sulphate. The granulated sodium bisulphate was completely stable.
EXAMPLE 7.
Example 5 was repeated, except that no calcium sulphate was added and that 22% by weight of the quantity of marine salt was replaced by non-purified industrial rock salt.
The result was the same as in Example 5.
EXAMPLE 8.
4000 kg per hour of sodium sulphate melt
(content of sodium bisulphate 96.5%) were
produced in the circulation reactor. The melt
was sprayed in the cooling tower (quantity of
steam 20 kg per hour) by means of bi
component nozzles. The product obtained was
substantialy stable and could be further pro
cessed without difficulty (water content: 0.15%).
EXAMPLE 9.
1100 1 of technical grade sulphuric acid
(d=1.84) and 1200 kg of marine salt were
fed into the circulation reactor per hour. The
temperature of the melt was 260 when 210
m3/hour of hydrogen were burnt with the air.
On its way to the spraying tower the melt was cooled to 220″C by a cooled tube mounted directly before the spraying nozzles. The
granules were cooled to 40″C by cooling air
in the spraying tower. The product only had
a moderate tendency to get sticky and could be further processed without essential difficulties.
WHAT WE CLAIM IS: 1. A process for the preparation of sodium bisulphate which comprises reacting sodium chloride and/or sodium sulphate with sulphuric acid in a reactor charged with molten sodium bisulphate, the reactor being heated by an immersion heater whereby combustion gases are formed, and the molar ratio of Na: S (as hereinbefore defined) in the melt being in the range of from 1.01:1 to 1.07:1.

2. A process as claimed in claim 1, wherein the molar ratio of Na: S is in the range of from 1.02:1 to 1.06:1.

3. A process as claimed in either claim 1 or claim 2, wherein the reaction is carried out in a circulation reactor which recycles the melt.

4. A process as claimed in claim 3, wherein the combustion gases from the immersion heater and the reaction gases are drawn off from the reactor at different points.

5. A process as claimed in any one of claims 1 to 4, wherein the combustion gases from the immersion heater are washed and the conductivity of the washing water is subsequently determined.

6. Aprocess as claimed in any one of claims 1 to 5, wherein the molten sodium bisulphate is withdrawn and subsequently granulated.

7. A process as claimed in claim 1, carried out substantially as described herein with reference to, and as illustrated by, the accompanying drawing.

8. A process as claimed in any one of claims 1 to 7, wherein the molten sodium bisulphate is granulated and subsequently held for at
least one minute at a temperature in the range of from 60 to 140″C.

9. A process as claimed in claim 8, wherein the granules are held at a temperature in the range of from 120 to 140″C.

10. A process as claimed in any one of claims 1 to 9, wherein the molten sodium bisulphate is granulated in the presence of from 0.1 to 5% by weight of finely divided calcium sulphate, magnesium sulphate, barium sulphate, sodium sulphate or sodium bi sulphate or a mixture of two or more such compounds, the compound or compounds being present before granulation.

11. A process as claimed in claim 10, where in the sodium bisulphate is prepared by reacting non-purified rock salt with sulphuric acid in a melt of sodium bisulphate, whereby magnesium sulphate and calcium sulphate present in the rock salt are incorporated in the molten sodium bisulphate.

12. A process as claimed in any one of claims 1 to 11, wherein the molten sodium bisulphate is granulated in the presence of from 0.01 to 3% by weight of water.

13. A process as claimed in any one of claims 1 to 12, wherein the temperature of the molten sodium bisulphate is adjusted to be in the range of from 186 to 236″C and the melt
is subsequently granulated from this
temperature.

14. A process as claimed in claim 13, wherein the melt is sprayed in a cooling tower whereby it solidifies during the free fall.

15. A process as claimed in claim 1, carried out substantially as described in any one of the Examples herein.

16. Sodium bisulphate, whenever prepared by a process as claimed in any one of claims
1 to 15.

17. A process for the continuous preparation of sodium bisulphate from sodium chloride or sodium sulphate and sulphuric acid in molten sodium bisulphate in a circulation reactor which circulates the melt, by heating the reactor directly by means of an immersion heater whereby combustion gases are formed, and withdrawing evolved hydrogen chloride and combustion gases at different places, which comprises maintaining in the melt a molar ratio of Na+/SO4- of from 1.07 to 1.01.

GB18660/77A
1976-05-05
1977-05-04
Process for the preparation of sodium bisulphate

Expired

GB1584702A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

DE2619811A

DE2619811C2
(en)

1976-05-05
1976-05-05

Process for the production of sodium bisulfate

Publications (1)

Publication Number
Publication Date

GB1584702A
true

GB1584702A
(en)

1981-02-18

Family
ID=5977112
Family Applications (3)

Application Number
Title
Priority Date
Filing Date

GB43993/79A
Expired

GB1584704A
(en)

1976-05-05
1977-05-04
Process for the preparation of sodium bisulphate granules

GB38193/79A
Expired

GB1584703A
(en)

1976-05-05
1977-05-04
Process for the preparation of sodium bisulphate granules

GB18660/77A
Expired

GB1584702A
(en)

1976-05-05
1977-05-04
Process for the preparation of sodium bisulphate

Family Applications Before (2)

Application Number
Title
Priority Date
Filing Date

GB43993/79A
Expired

GB1584704A
(en)

1976-05-05
1977-05-04
Process for the preparation of sodium bisulphate granules

GB38193/79A
Expired

GB1584703A
(en)

1976-05-05
1977-05-04
Process for the preparation of sodium bisulphate granules

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JP
(1)

JPS52133899A
(en)

BE
(1)

BE854299A
(en)

DE
(1)

DE2619811C2
(en)

FR
(2)

FR2350302A1
(en)

GB
(3)

GB1584704A
(en)

IT
(1)

IT1075526B
(en)

Cited By (2)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US7067094B2
(en)

2003-09-09
2006-06-27
Grillo-Werke Ag
Process for the brightening of sodium hydrogensulfate

CN116924344A
(en)

2023-09-15
2023-10-24
潍坊石大昌盛能源科技有限公司
Granulating method of sodium hydrosulfide

Families Citing this family (2)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

DE2810693C2
(en)

1978-03-11
1982-07-15
Hoechst Ag, 6000 Frankfurt

Process for the continuous production of sodium bisulfate

CN102153111B
(en)

2011-02-28
2012-07-04
绍兴市东湖生化有限公司
Method for preparing anhydrous sodium hydrogen sulfate by using ethephon production waste liquid

1976

1976-05-05
DE
DE2619811A
patent/DE2619811C2/en
not_active
Expired

1977

1977-05-03
IT
IT23136/77A
patent/IT1075526B/en
active

1977-05-04
GB
GB43993/79A
patent/GB1584704A/en
not_active
Expired

1977-05-04
JP
JP5085677A
patent/JPS52133899A/en
active
Pending

1977-05-04
GB
GB38193/79A
patent/GB1584703A/en
not_active
Expired

1977-05-04
GB
GB18660/77A
patent/GB1584702A/en
not_active
Expired

1977-05-05
FR
FR7713684A
patent/FR2350302A1/en
active
Granted

1977-05-05
BE
BE177303A
patent/BE854299A/en
not_active
IP Right Cessation

1977-11-09
FR
FR7733729A
patent/FR2392935A1/en
active
Granted

Cited By (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US7067094B2
(en)

2003-09-09
2006-06-27
Grillo-Werke Ag
Process for the brightening of sodium hydrogensulfate

CN116924344A
(en)

2023-09-15
2023-10-24
潍坊石大昌盛能源科技有限公司
Granulating method of sodium hydrosulfide

CN116924344B
(en)

2023-09-15
2023-11-17
潍坊石大昌盛能源科技有限公司
Granulating method of sodium hydrosulfide

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FR2350302A1
(en)

1977-12-02

DE2619811B1
(en)

1977-09-15

IT1075526B
(en)

1985-04-22

DE2619811C2
(en)

1978-05-11

FR2392935B1
(en)

1983-01-07

FR2350302B1
(en)

1983-01-14

JPS52133899A
(en)

1977-11-09

GB1584703A
(en)

1981-02-18

FR2392935A1
(en)

1978-12-29

GB1584704A
(en)

1981-02-18

BE854299A
(en)

1977-11-07

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