Formic acid 85 wt% by methanol carbonylation and methyl formate hydrolysis (50 kt/a)

Methanol and carbon monoxide form methyl formate over sodium methoxide; the ester is hydrolysed with water, methyl formate and methanol are recycled, and the aqueous acid is concentrated to 85 wt% by pressure-swing distillation. Concept stage, assumed basis, preliminary gate-to-gate LCI.

Calculation maturity: not assessedDesign maturity: Concept (research)Not independently reviewedOxygenates Report a problem with this process

Research outputNot engineering advice and not an approved design: do not use it for construction, operation or safety decisions. What this means

Carbon monoxide (from a syngas cold box outside the boundary) is compressed to 4.6 MPa and absorbed into recycled methanol with 2.5 wt% sodium methoxide in a gas-liquid loop reactor at 353 K; 30 % of the methanol is converted per pass and the CO-rich vent (8 % of the CO fed) is burnt in a thermal oxidiser. Methyl formate is distilled off and hydrolysed at 393 K with water (1.5 mol/mol), autocatalysed by recycled formic acid, to 95 % (assumed) of the equilibrium conversion (28.9 % per pass). Unreacted ester and the methanol formed are distilled off and recycled; the methanol returns dry to the carbonylation, so only losses are made up. The dilute acid (49 wt%) is concentrated by pressure-swing distillation across the maximum-boiling formic acid / water azeotrope: a 203 kPa(a) column takes water overhead (recycled to the hydrolysis) and a 12 kPa(a) column gives the 85 wt% product overhead, its 66 wt% bottoms returning to the hydrolyser as catalyst.

The reactors are conversion models from open patents (US4216339A, EP2747883A1, EP3661904B1, US4299981); separators and columns are specified splits and every duty a shortcut estimate from an independent script (scripts/balance.py), because no property package of core covers this liquid system. See DESIGN.md for every assumption and gated step.

Capacity: 6.25 t/h formic acid 85 wt% (50 kt/a), ASSUMED
Operation: 8,000 h/a
Location: generic (not chosen)
Engineering gates: Concept and feasibility (no results yet)
Maintainers: Artur Schweidtmann

Design basis and assumptions (5)

Carbonylation at 353 K, 4500 kPa(a), 2.5 wt% sodium methoxide, 30 % methanol conversion per pass and 92 mol% CO yield (US4216339A Example 1; D-005).
Hydrolysis at 393 K, 600 kPa(a), water/methyl formate 1.5 mol/mol, 95 % (ASSUMED) of the equilibrium conversion with Kx = 0.20 (EP2747883A1, EP3661904B1; US4299981 an unverified lead; D-008): 28.9 % per pass.
Pressure-swing concentration: C-301 at 203 kPa(a) to 77 wt% (azeotrope about 80 wt%), C-302 at 12 kPa(a) to 85 wt% overhead and 66 wt% bottoms recycled to the hydrolyser (EP3661904B1, EP2747883A1; D-009).
All column splits are sharp except the stated methanol in the methyl formate distillates and the 0.5 wt% acid in the C-301 water (D-007..D-009); reverse esterification and formic acid decomposition neglected (D-008).
Duties are shortcut estimates ((R+1) D dHvap, ASSUMED reflux ratios, C-301 at 1.2 times its estimated minimum, no heat integration; D-011); total LP steam heat 4.46 kWh/kg product, about 1.9 times the 2400 kWh/t of prior art quoted in EP2747883A1.

From process/design-basis.yaml.

Engineering model

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Snapshot of c3ab348, cheme-as-code 1.6.0.

What goes in and out

In

Carbon monoxideFeedstockfeed:CO: carbon monoxide from a syngas cold box outside the boundary, 0.568 kg/kg product
MethanolFeedstockfeed:MEOH: methanol make-up (e.g. methanol-1), 0.012 kg/kg
Sodium methoxideFeedstockfeed:CAT: catalyst: sodium methoxide 30 wt% in methanol, counted by mass of the solution
WaterFeedstockDemineralised hydrolysis make-up water, 0.483 kg/kg product
AirFeedstockCombustion air of the vent oxidiser, 0.235 kg/kg product

Out

Formic acidMain productFormic acid 85 wt% to storage, counted by mass of the solution
Carbon dioxideEmission72.4 g/kg product, from burning the carbonylation vent (unreacted CO) in the oxidiser (fossil)

Utilities: Electricity (84 Wh/kg product: CO compressor (89 %), pumps, vacuum system (ASSUMED efficiencies)), Steam (4.46 kWh heat/kg product as LP steam (450 kPa(a)): reboilers of five columns, hydrolyser feed preheat (shortcut, no heat integration, D-011)), Cooling water (3.61 kWh/kg product removed, 25/35 C (ASSUMED))

Show in the process graph

Reactions

Id	As written	Reaction	Other processes
CARB	CH3OH + CO ⇌ HCOOCH3	CH₄O+COin equilibrium withC₂H₄O₂
CO_COMB	CO + 1/2 O2 → CO2	2CO+O₂gives2CO₂	7 other processes
DEACT	NaOCH3 + H2O + CO → HCOONa + CH3OH	CH₃NaO+H₂O+COgivesCHNaO₂+CH₄O
HYD	HCOOCH3 + H2O ⇌ HCOOH + CH3OH	C₂H₄O₂+H₂Oin equilibrium withCH₂O₂+CH₄O
MEOH_COMB	CH3OH + 3/2 O2 → CO2 + 2 H2O	2CH₄O+3O₂gives2CO₂+4H₂O	1 other process
MF_COMB	HCOOCH3 + 2 O2 → 2 CO2 + 2 H2O	C₂H₄O₂+2O₂gives2CO₂+2H₂O

Each reaction's page has the conversion, heat of reaction, catalyst and sources this process states, next to those of other processes with the same reaction. All reactions

Life cycle assessment

Footprint not publishedThe process changed since the LCA was last run; its values return once it is run again. Method, functional unit and inventory are below.

Method and data

Goal: Preliminary gate-to-gate life cycle inventory of formic acid 85 wt% made by methanol carbonylation and methyl formate hydrolysis with pressure-swing concentration, at the concept stage: which raw materials, utilities, wastes and emissions the plant exchanges per kg of product, as the foreground for a later cradle-to-gate study. No impact results: the backgrounds are not mapped yet (D-012).
Functional unit: 1 kg Formic acid 85 wt% (1 kg formic acid)
Boundary: cradle-to-gate
Characterisation: Factors kept with the process · GWP100
Data quality: Published factors
Result: partial screening carbon footprint · 8 data gaps

Inventory per 1 kg Formic acid 85 wt% (19 flows)

Flow	Phase	Direction	Quantity	Unit	Provenance
Carbon monoxide (from a syngas cold box outside the boundary)	operation	input	0.5685	kg	assumed
Methanol make-up (methanol-1)	operation	input	0.01246	kg	assumed
Sodium methoxide 30 wt% in methanol	operation	input	0.002319	kg	assumed
Process water (demineralised)	operation	input	0.4828	kg	assumed
Combustion air	operation	input	0.2349	kg	assumed
Electric power	operation	input	0.0843	kWh	assumed
Low-pressure steam (450 kPa(a), saturated)	operation	input	4.463	kWh	assumed
Formic acid 85 wt% to storage	operation	output	1	kg	assumed
Spent catalyst purge (sodium formate and methoxide in methanol) to incineration	operation	output	0.0141	kg	calculated
Oxidiser flue gas to stack	operation	output	0.2868	kg	calculated
Cooling water return	operation	output	4.488	kWh	assumed
AR to the environment	operation	output	0.003013	kg	calculated
CO to the environment	operation	output	0.00004492	kg	calculated
CO2 to the environment	operation	output	0.07239	kg	calculated
H2O to the environment	operation	output	0.0009458	kg	calculated
MEOH to the environment	operation	output	0.0000003179	kg	calculated
MF to the environment	operation	output	0.0000009821	kg	calculated
N2 to the environment	operation	output	0.1832	kg	calculated
O2 to the environment	operation	output	0.02721	kg	calculated

Computed by ChemE-as-Code from lca/README.md, lca/dataset.yaml, lca/factors.yaml, lca/gaps.csv, lca/inventory.csv, lca/lca.yaml, lca/mappings.yaml, lca/results.csv, lca/results.md.

In the open LCI database (cheme-as-code-atlas-preview-c3ab348) as Formic acid 85 wt% to storage Preliminary.

Download it for Brightway, openLCA and other tools.

In the LCI database: system model, datasets and KPIs against the benchmarks

In the LCI database

Status: Preliminary 4 unmapped exchanges. Some exchanges have no background mapping yet: they are exported unlinked and count no burden, so the inventory is incomplete.
System model: attributional, cut-off (methodology 1.1.0)
Allocation: mass (single-output, from default) · product:FA 100 %
Allocation findings: none
Change report: Not available: this build has no change report against an earlier release.
Dataset pages: Formic acid 85 wt% to storage Preliminary

KPI benchmark positions: not available (no benchmarked KPI for this process's datasets).

Maturity and review

Design maturity Concept (claimed): An idea or first flowsheet; numbers are rough. Concept PFD with closed mass, component and element balances on every block and step (cheme validate, cheme process streams), recycles of methyl formate, methanol, water and 66 wt% acid closed by scripts/balance.py. The reactors and the oxidiser are calculated by cheme (conversion model); core's equilibrium check puts the hydrolyser outlet just short of the sourced Kx = 0.20 (ln Q/K = -0.11). Separator and column outlets are specified splits; duties are shortcut estimates with assumed reflux ratios (C-301 at 1.2 times a shortcut minimum reflux) and no heat integration (4.46 kWh LP steam heat per kg product, about 1.9 times the 2400 kWh/t of prior art quoted in EP2747883A1). The energy balance is not evaluable in core: no property package covers the liquid methanol / methyl formate / water / formic acid system and the liquid-reactor energy basis is not verified. Capacity, feed purities, reflux ratios and the purge fraction are assumed. cheme maturity reaches no calculation level (feeds and the hydrolysis and oxidiser conversions are assumed), so `maturity: concept` is claimed as the lowest level the manifest allows, not as evidence-backed (DESIGN.md D-014). Preliminary gate-to-gate LCI with every background unmapped (gaps). Not reviewed. Main products and feeds are listed under chemistry with their chemicals registry entries (issue #251).

Calculation maturity, from the checked evidenceNot assessed

The process has no maturity report (cheme maturity, checks/maturity.json), so no calculation maturity is established.

No level shownThe design maturity (Concept) is the manifest's claim, not evidence. A level appears here once the process's repository holds a current report from cheme maturity --write.

Artifact completeness

Which deliverables exist. They never raise a calculation maturity level: a drawing from unchecked numbers is still unchecked.

Not reported without a maturity report.

Independent review

Not independently reviewed

No independent engineering review yet. Automated checks passing is not a review.

Set by people only. Reaching a calculation maturity level or passing automated checks is not an independent review or an approval.

Where the evidence comes from

Report: processes/formic-acid-1/checks/maturity.json (not in the library)
Design basis: process/design-basis.yaml
Method: How ChemE-as-Code checks the levels (requirement by requirement)

Open items

0 open items · 0 closed

New action item New engineering hold New technical query New design change All issues

Sources

Engineering project: Formic acid (methyl formate hydrolysis) · cheme-as-code>=0.8
Library version: c3ab348 (process last changed in c3ab348)
Drawings rendered by: cheme 1.6.0 (pyDEXPI 2.1.0)
Data: Catalog record (JSON) · CC-BY-4.0
Files: View the files on GitHub · change history and authors

References

UCB SA (1980) US4216339A: Process for the production of methyl formate (Couteau, Ramioulle)
Taminco BV (2014) EP2747883A1: Process of formic acid production by hydrolysis of methyl formate (Pasek, Trejbal, Roose)
Eastman Chemical Co. (2020/2026) EP3661904B1: Process for producing formic acid using low-boiling formate esters
US4299981: Preparation of formic acid by hydrolysis of methyl formate (claims and abstract only, via search)
Formic Acid. Ullmann's Encyclopedia of Industrial Chemistry (issue lead; not read, licensed) · doi:10.1002/14356007.a12_013.pub3

How to cite

For the data, cite the Process Atlas paper; for the platform that builds and checks it, the ChemE-as-Code paper.

Schweidtmann, A. M. & Weber, J. M. (2026, in preparation). Process Atlas: an open, git-native, reproducible library and life cycle inventory of chemical processes (working title).

For this process: "Formic acid 85 wt% by methanol carbonylation and methyl formate hydrolysis (50 kt/a)", ChemE-as-Code process library, version c3ab348.

BibTeX

@unpublished{schweidtmann_process_atlas,
  author = {Schweidtmann, Artur M. and Weber, Jana M.},
  title = {{Process Atlas: an open, git-native, reproducible library and life cycle inventory of chemical processes (working title)}},
  year = {2026},
  url = {https://atlas.cheme-as-code.org},
  note = {in preparation}
}

Schweidtmann, A. M. (2026, in preparation). ChemE-as-Code: An Open-Source Platform for AI-Accelerated Chemical Process Engineering (working title).